Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts

ABSTRACT

The present invention relates to novel hexacoordinated metathesis catalysts and to methods for making and using the same. The inventive catalysts are of the formula                    
     wherein: 
     M is ruthenium or osmium; 
     X and X 1  are the same or different and are each independently an anionic ligand; 
     L, L 1′  and L 2  are the same or different and are each independently a neutral electron donor ligand; and, 
     R and R 1  are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20  alkyl, C 2 -C 20  alkenyl, C 2 -C 20  alkynyl, aryl, C 1 -C 20  carboxylate, C 1 -C 20  alkoxy, C 2 -C 20  alkenyloxy, C 2 -C 20  alkynyloxy, aryloxy, C 2 -C 20  alkoxycarbonyl, C 1 -C 20  alkylthio, C 1 -C 20  alkylsulfonyl and C 1 -C 20  alkylsulfinyl and silyl. Optionally, each of the R or R 1  substituent group may be substituted with one or more moieties selected from the group consisting of C 1 -C 10  alkyl, C 1 -C 10  alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a C 1 -C 5  alkyl, C 1 -C 5  alkoxy, and phenyl. Moreover, any of the catalyst ligands may further include one or more functional groups. Examples of suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl. In certain embodiments, at least one of L, L 1′  and L 2  is an N-heterocyclic carbene ligand.

This application claims the benefit of U.S. Provisional PatentApplication No. 60/314,978 filed Aug. 24, 2001; is a CIP U.S.application Ser. No. 10/017,489 filed Dec. 14, 2001; U.S. applicationSer. No. 10/107,531 filed Mar. 25, 2002; U.S. application Ser. No.10/138,188 filed May 3, 2002; U.S. Provisional Application No.60/309,806 filed Aug. 1, 2001 and, U.S. patent application Ser. No.09/948,115, filed Sep. 5, 2001, the contents of each of which areincorporated herein by reference.

The U.S. Government has certain rights in this invention pursuant toGrant No. CHE-9809856 awarded by the National Science Foundation.

BACKGROUND

Metathesis catalysts have been previously described by for example, U.S.Pat. Nos. 5,312,940, 5,342,909, 5,728,917, 5,750,815, 5,710,298, and5,831,108 and PCT Publications WO 97/20865 and WO 97/29135 which are allincorporated herein by reference. These publications describewell-defined single component ruthenium or osmium catalysts that possessseveral advantageous properties. For example, these catalysts aretolerant to a variety of functional groups and generally are more activethan previously known metathesis catalysts. Recently, the inclusion ofan N-heterocyclic carbene (NHC) ligand, such as an imidazolidine ortriazolylidene ligand as described in U.S. application Ser. Nos.09/539,840, 09/576,370 and PCT Publication No. WO 99/51344, the contentsof each of which are incorporated herein by reference, in thesemetal-carbene complexes has been found to improve the alreadyadvantageous properties of these catalysts. In an unexpected andsurprising result, the shift in structure from the well-establishedpenta-coordinated catalyst structure to the hexacoordinated catalyststructure has been found to significantly improve the properties of thecatalyst. For example, these hexacoordinated catalysts of the presentinvention exhibit increased activity and selectivity not only in ringclosing metathesis (“RCM”) reactions, but also in other metathesisreactions including cross metathesis (“CM”) reactions, reactions ofacyclic olefins, and ring opening metathesis polymerization (“ROMP”)reactions.

SUMMARY

The present invention relates to novel hexacoordinated metathesiscatalysts and to methods for making and using the same. The inventivecatalysts are of the formula

wherein:

M is ruthenium or osmium;

X and X¹ are the same or different and are each independently an anionicligand;

L, L^(1′) and L² are the same or different and are each independently aneutral electron donor ligand; and,

R and R¹ are each independently hydrogen or a substituent selected fromthe group consisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀alkylsulfonyl, C₁-C₂₀ alkylsulfinyl, and silyl. Optionally, each of theR or R¹ substituent group may be substituted with one or more moietiesselected from the group consisting of C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, andaryl which in turn may each be further substituted with one or moregroups selected from a halogen, a C₁-C₅ alkyl, C₁-C₅ alkoxy, and phenyl.Moreover, any of the catalyst ligands may further include one or morefunctional groups. Examples of suitable functional groups include butare not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester,ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen,alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate,cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

In preferred embodiments, L² and L^(1′) are pyridine and L is aphosphine or an N-heterocyclic carbene ligand. Examples ofN-heterocyclic carbene ligands include:

wherein R, R¹ R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are each independentlyhydrogen or a substituent selected from the group consisting of C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl, C₁-C₂₀alkylsulfinyl and silyl. Optionally, each of the R, R¹ R⁶, R⁷, R⁸, R⁹,R¹⁰ and R¹¹ substituent group may be substituted with one or moremoieties selected from the group consisting of C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, and aryl which in turn may each be further substituted with oneor more groups selected from a halogen, a C₁-C₅ alkyl, C₁-C₅ alkoxy, andphenyl. Moreover, any of the catalyst ligands may further include one ormore functional groups. Examples of suitable functional groups includebut are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde,ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen,alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate,cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.The inclusion of an NHC ligand to the hexacoordinated ruthenium orosmium catalysts has been found to dramatically improve the propertiesof these complexes. Because the NHC-based hexacoordinated complexes areextremely active, the amount of catalysts that is required issignificantly reduced.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention generally relates to ruthenium and osmium carbenecatalysts for use in olefin metathesis reactions. More particularly, thepresent invention relates to hexacoordinated ruthenium and osmiumcarbene catalysts and to methods for making and using the same. Theterms “catalyst” and “complex” herein are used interchangeably.

Unmodified ruthenium and osmium carbene complexes have been described inU.S. Pat. Nos. 5,312,940, 5,342,909, 5,728,917, 5,750,815, and5,710,298, all of which are incorporated herein by reference. Theruthenium and osmium carbene complexes disclosed in these patents allpossess metal centers that are formally in the +2 oxidation state, havean electron count of 16, and are penta-coordinated. These catalysts areof the general formula

wherein:

M is ruthenium or osmium;

X and X¹ are each independently any anionic ligand;

L and L¹ are each independently any neutral electron donor ligand;

R and R¹ are the same or different and are each independently hydrogenor a substituent selected from the group consisting of C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy,C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl,C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl, C₁-C₂₀ alkylsulfinyl, and silyl.Optionally, each of the R or R¹ substituent group may be substitutedwith one or more moieties selected from the group consisting of C₁-C₁₀alkyl, C₁-C₁₀ alkoxy, and aryl which in turn may each be furthersubstituted with one or more groups selected from a halogen, a C₁-C₅alkyl, C₁-C₅ alkoxy, and phenyl. Moreover, any of the catalyst ligandsmay further include one or more functional groups. Examples of suitablefunctional groups include but are not limited to: hydroxyl, thiol,thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro,carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine,imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine,sulfone, sulfide, and sulfenyl.

The catalysts of the present invention are similar in that they are Ruor Os complexes; however, in these complexes, the metal is formally inthe +2 oxidation state, and has an electron count of 18 and arehexacoordinated. These catalysts are of the general formula:

wherein

M is ruthenium or osmium;

X and X¹ are the same or different and are each independently anyanionic ligand;

L, L^(1′), and L² are the same or different and are each independentlyany neutral electron donor ligand;

R and R¹ are the same or different and are each independently hydrogenor a substituent selected from the group consisting of C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy,C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl,C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl, C₁-C₂₀ alkylsulfinyl, and silyl.Optionally, each of the R or R¹ substituent group may be substitutedwith one or more moieties selected from the group consisting of C₁-C₁₀alkyl, C₁-C₁₀ alkoxy, and aryl which in turn may each be furthersubstituted with one or more groups selected from a halogen, a C₁-C₅alkyl, C₁-C₅ alkoxy, and phenyl. Moreover, any of the catalyst ligandsmay further include one or more functional groups. Examples of suitablefunctional groups include but are not limited to: hydroxyl, thiol,thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro,carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine,imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine,sulfone, sulfide, and sulfenyl.

The hexacoordinated complex provides several advantages over thewell-known pentacoordinated complexes. For example, the hexacoordinatedcomplexes have greater air stability in the solid state because they arecoordinatively saturated. Due to the lability of the additional ligand,e.g. pyridines, the complexes initiate faster than the phosphine basedpentacoordinated species. Slow initiation means that only a small amountof complex is actually catalystically active thereby wasting much of theadded complex. With faster initiators, catalyst loading is lowered.Further, and without being bound by theory, it is believed that theslower propogation of the hexacoordinated complexes, due to there-binding of the labile ligands relative to the phosphines, translatesto lower polydisperity. Moreover, the coordinatively saturated speciescrystallize better than their pentacoordinated counterparts. Inaddition, due to the lability of the ligands in the hexacoordinatedcomplexes (e.g. pyridines and chlorines), these complexes allow accessto previously inaccessible complexes and provide with higher puritycertain complexes that can be obtained through different routes. Forexample, the pentacoordinated benzylidene with triphenylphosphine as itsphosphine ligand can be prepared in higher yield and with greater purityusing the hexacoordinated complex. The pentacoordinated benzylidene withP(p-CF₃C₆H₄)₃ as its phosphine ligand is inaccessible through existingroutes. Without being bound by theory, it is believe that this isbecause it would require the substitution of a stronger donor ligandwith a weaker donor ligand. Substitution of the anionic ligands of thehexacoordinated complexes is much more rapid than with the correspondingpentacoordinated species (e.g. phosphine bound). Without being bound bytheory, it is believed that this results from the requirement of liganddissociation before anionic ligand substitution. Thus complexes withfast dissociation of their neutral electron donor ligands will undergofaster substitution.

The catalysts of the invention are also useful for ring-openingmetathesis polymerization (ROMP), ring-closing metathesis (RCM), ADMET,and cross-metathesis. The synthesis and polymerization of olefins viathese metathesis reactions can be found in, for example, U.S.application Ser. No. 09/891,144 entitled: “Synthesis of Functionalizedand Unfunctionalized Olefins, filed Jun. 25, 2001, and U.S. applicationSer. No. 09/491,800, the contents of each of which are incorporatedherein by reference. Preferred embodiments of the catalysts of theinvention possess at least one NHC ligand attached to the metal center,as illustrated by the following general formula:

In preferred embodiments of the inventive catalysts, the R substituentis hydrogen and the R¹ substituent is selected from the group consistingof C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and aryl. In even more preferredembodiments, the R¹ substituent is phenyl or vinyl, optionallysubstituted with one or more moieties selected from the group consistingof C₁-C₅ alkyl, C₁-C₅ alkoxy, phenyl, and a functional group. Inespecially preferred embodiments, R¹ is phenyl or vinyl substituted withone or more moieties selected from the group consisting of chloride,bromide, iodide, fluoride, —NO₂, —NMe₂, methyl, methoxy and phenyl. Inthe most preferred embodiments, the R¹ substituent is phenyl or—C═C(CH₃)₂. When R¹ is vinyl, the catalyst is of the general formula:

wherein M, L, L¹, L^(1′), L², X, X¹, and R are as defined above. R′ andR″ are preferably independently hydrogen or phenyl but can be selectedfrom any of the groups listed for R or R¹.

In preferred embodiments of the inventive catalysts, X and X¹ are eachindependently hydrogen, halide, or one of the following groups: C₁-C₂₀alkyl, aryl, C₁-C₂₀ alkoxide, aryloxide, C₃-C₂₀ alkyldiketonate,aryldiketonate, C₁-C₂₀ carboxylate, arylsulfonate, C₁-C₂₀alkylsulfonate, C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl, or C₁-C₂₀alkylsulfinyl. Optionally, X and X¹ may be substituted with one or moremoieties selected from the group consisting of C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, and aryl which in turn may each be further substituted with oneor more groups selected from halogen, C₁-C₅ alkyl, C₁-C₅ alkoxy, andphenyl. In more preferred embodiments, X and X¹ are halide, benzoate,C₁-C₅ carboxylate, C₁-C₅ alkyl, phenoxy, C₁-C₅ alkoxy, C₁-C₅ alkylthio,aryl, and C₁-C₅ alkyl sulfonate. In even more preferred embodiments, Xand X¹ are each halide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO,(CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO, MeO, EtO, tosylate, mesylate, ortrifluoromethanesulfonate. In the most preferred embodiments, X and X¹are each chloride.

L, L¹, L^(1′) and L² may be any appropriate monodentate or multidentateneutral electron donor ligands. Multidentate neutral electron donorligands include bidentate, tridentate, or tetradentate neutral electrondonor ligands, for example. In preferred embodiments of the inventivecatalysts, L, L¹, L^(1′) and L² are each independently selected from thegroup consisting of phosphine, sulfonated phosphine, phosphite,phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine,sulfoxide, carboxyl, nitrosyl, pyridine, and thioether, or anyderivatives therefrom. At least one L, L¹, L^(1′) and L² may also be anN-heterocyclic carbene ligand. Preferred embodiments include complexeswhere both L¹ and L² are either the same or different NHC ligands.

In preferred embodiments, at least one of L, L¹, L^(1′) and L² is aphosphine of the formula PR³R⁴R⁵, where R³, R⁴, and R⁵ are eachindependently aryl or C₁-C₁₀ alkyl, particularly primary alkyl,secondary alkyl or cycloalkyl. In the even more preferred embodiments,at least one of L, L¹, L^(1′) and L² is each selected from the groupconsisting of —P(cyclohexyl)₃, —P(cyclopentyl)₃, —P(isopropyl)₃, and—P(phenyl)₃. Even more preferably, at least one of L, L¹, L^(1′) and L²is an NHC ligand. A preferred embodiment include where L is an NHC, L¹is P(cyclohexyl)₃ or —P(cyclopentyl)₃, and L^(1′) and L² are eachheterocyclic ligands, optionally aromatic, or together form a bidenatateligand. Preferably L^(1′) and L² are each independently pyridine or apyridine derivative.

Examples of NHC ligands include ligands of the general formulas:

wherein R, R¹, R′, R″, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are eachindependently hydrogen or a substituent selected from the groupconsisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy,aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl,C₁-C₂₀ alkylsulfinyl, and silyl. Optionally, each of the R, R¹ R⁶, R⁷,R⁸, R⁹, R¹⁰, and R¹¹ substituent group may be substituted with one ormore moieties selected from the group consisting of C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, and aryl which in turn may each be further substituted with oneor more groups selected from a halogen, a C₁-C₅ alkyl, C₁-C₅ alkoxy, andphenyl. Moreover, any of the catalyst ligands may further include one ormore functional groups. Examples of suitable functional groups includebut are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde,ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen,alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate,cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

In preferred embodiments, R⁶, R⁷, R⁸ and R⁹ are independently selectedfrom the group consisting of hydrogen, phenyl, or together form acycloalkyl or an aryl optionally substituted with one or more moietiesselected from the group consisting of C₁-C₁₀alkyl, C₁-C₁₀alkoxy, aryl,and a functional group selected from the group consisting of hydroxyl,thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide,nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, carbamate, and halogen; and R¹⁰ and R¹¹ are each isindependently C₁-C₁₀ alkyl or aryl optionally substituted with C₁-C₅alkyl, C₁-C₅ alkoxy, aryl, and a functional group selected from thegroup consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester,ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen,alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate,cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.

In more preferred embodiments, R⁶ and R⁷ are both hydrogen or phenyl, orR⁶ and R⁷ together form a cycloalkyl group; R⁸ and R⁹ are hydrogen andR¹⁰ and R¹¹ are each either substituted or unsubstituted aryl. Withoutbeing bound by theory, it is believed that bulkier R¹⁰ and R¹¹ groupsresult in catalysts with improved characteristics such as thermalstability. In especially preferred embodiments, R¹⁰ and R¹¹ are the sameand each is independently of the formula:

wherein:

R¹², R¹³, and R¹⁴ are each independently hydrogen, C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, aryl, or a functional group selected from hydroxyl, thiol,thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro,carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide,carboalkoxy, carbamate, and halogen. In especially preferredembodiments, R¹², R¹³, and R¹⁴ are each independently selected from thegroup consisting of hydrogen, methyl, ethyl, propyl, isopropyl,hydroxyl, and halogen. In the most preferred embodiments, R¹², R¹³, andR¹⁴ are the same and are each methyl.

In these complexes, R⁶, R⁷, R⁸, and R⁹ are each independently hydrogenor a substituent selected from the group consisting of C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy,C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl,C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl and C₁-C₂₀ alkylsulfinyl.Imidazolidine ligands are also referred to as imidizol-2-ylideneligands.

Other examples of neutral electron donor ligands include ligands whichare derived, for example, from unsubstituted or substituted heteroarenessuch as furan, thiophene, pyrrole, pyridine, bipyridine, picolylimine,gamma-pyran, gamma-thiopyran, phenanthroline, pyrimidine, bipyrimidine,pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran,dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole,dithiazole, isoxazole, isothiazole, quinoline, bisquinoline,isoquinoline, bisisoquinoline, acridine, chromene, phenazine,phenoxazine, phenothiazine, triazine, thianthrene, purine, bisimidazoleand bisoxazole.

Examples of substituents are OH, halogen, C(O)OR_(s1), OC(O)R_(s4),C(O)R_(s2), nitro, NH₂, cyano, SO₃M_(y), OSO₃M_(y), NR₂OSO₃M_(y),N═N—R_(s2), C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₁-C₁₂ alkoxy, C₃-C₁₂cycloalkyl, C₃-C₁₂ cycloalkenyl, C₁₂-C₁₁ heterocycloalkyl, C₂-C₁₁heterocycloalkenyl, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy, C₅-C₉ heteroaryl, C₅-C₉heteroaryloxy, C₇-C₁₁ aralkyl, C₇-C₁₁ aralkyloxy, C₆-C₁₀ heteroaralkyl,C₈-C₁₁ aralkenyl, C₇-C₁₀ heteroaralkenyl, monoamino, diamino, sulfonyl,sulfonamide, carbamide, carbamate, sulfohydrazide, carbohydrazide,carbohydroxamic acid residue and aminocarbonylamide, in which R_(s1) ishydrogen, M_(y), C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₂-C₁₁heterocycloalkyl, C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkyl orC₆-C₁₀ heteroaralkyl, R₁₄ is hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl,C₃-C₁₂ cycloalkyl, C₂-C₁₁ heterocycloalkyl, C₁₆-C₁₀ aryl, C₅-C₁₉heteroaryl, C₇-C₁₁ aralkyl or C₆-C₁₀ heteroaralkyl, and R_(s2) andR_(s20) are hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl,C₃-C₁₂ cycloalkenyl, C₂-C₁₁ heterocycloalkyl, C₁-C₁₁ heterocycloalkenyl,C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkyl, C₆-C₁₀ heteroaralkyl,C₈-C₁₁ aralkenyl or C₇-C₁₀ heteroaralkenyl, and alkyl, alkenyl, alkoxy,cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl,aryloxy, heteroaryl, heteroaryloxy, aralkyl, aralkyloxy, heteroaralkyl,aralkenyl and heteroaralkenyl in turn are unsubstituted or substitutedby one of the above-mentioned substituents; and y is 1 and M is amonovalent metal or y is ½ and M is a divalent metal.

In the context of the description of the present invention, the termsmetal and corresponding cations refer to an alkali metal, for exampleLi, Na or K, an alkaline earth metal, for example Mg, Ca or Sr, or Mn,Fe, Zn or Ag, and corresponding cations. Lithium, sodium and potassiumions, with their salts, are preferred. NH₂, monoamino, diamino,carbamide, carbamate, carbohydrazide, sulfonamide, sulfohydrazide andaminocarbonylamide correspond preferably to a group R₈C(O)(NH)_(p)N(R₉)—, —C(O)(NH)_(p)NR₈R₉, R₈OC(O)(NH)_(p)N(R₉)—,R₈R₄ONC(O)(NH)_(p)N(R₉)—, —OC(O)(NH)_(p)NR₈R₉, —N(R₄₀)C(O)(NH)_(p)NR₈R₉,R₈S(O)₂(NH) _(p)N(R₉)—; —S(O) 2 (NH)_(p)NR₈R₉; R₈R₄ONS(O)₂N(R₉)—or—NR₄OS(O)₂NR₈R₉, in which R₈, R₉ and R₄₀ independently of one anotherare hydrogen, OH, C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl,C₃-C₁₂ cycloalkenyl, C₂-C₁₁ heterocycloalkyl, C₂-C₁₁ heterocycloalkenyl,C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₆ aralkyl, C₈-C₁₆aralkenyl withC₂-C₆alkenylene and C₆-C₁₀ aryl, C₆-C₁₅ heteroaralkyl, C₆-C₁₅heteroaralkenyl, or di-C₆-C₁₀ aryl-C₁-C₆ alkyl, or R_(8′)R_(9′)N, inwhich R_(8′) and R_(9′) independently of one another are hydrogen, OH,SO₃M_(y), OSO₃M_(y), C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, C₂-C₁₁heterocycloalkyl, C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkyl, C₆-C₁₀heteroaralkyl, C₈-C₁₆ aralkenyl with C₂-C₆ alkenylene and C₆-C₁₀ aryl,or di-C₆-C₁₀ aryl-C₁-C₆ alkyl, which are unsubstituted or substituted byone or more substituents from the group consisting of OH, halogen,C(O)OR_(s1), OC(O)R_(s4), C(O)R_(s2), nitro, NH₂, cyano, SO₃Z_(y),OSO₃Z_(y), NR₂₀SO₃Z_(y), C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₁-C₁₂ alkoxy,C₃-C₁₂ cycloalkyl, C₃-C₁₂ cycloalkenyl, C₂-C₁₁ heterocycloalkyl, C₂-C₁₁heterocycloalkenyl, C₆-C₁₀ aryl, C₆-C₁₀aryloxy, C₅-C₉ heteroaryl, C₅-C₉heteroaryloxy, C₇-C₁₁ aralkyl, C₇-C₁₁ aralkyloxy, C₆-C₁₀ heteroaralkyl,C₈-C₁₁ aralkenyl, C₇-C₁₀ heteroaralkenyl, monoamino, diamino, sulfonyl,sulfonamide, carbamide, carbamate, sulfohydrazide, carbohydrazide,carbohydroxamic acid residue and aminocarbonylamide, in which R₁₁ ishydrogen, Z_(y), C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₂-C₁₁heterocycloalkyl, C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkyl orC₆-C₁₀ heteroaralkyl, R_(s4) is hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl,C₃-C₁₂ cycloalkyl, C₂-C₁₁ heterocycloalkyl, C₆-C₁₀ aryl, C₅-C₉heteroaryl, C₇-C₁₁ aralkyl or C₆-C₁₀ heteroaralkyl, and R_(s2) ishydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₃-C₁₂cycloalkenyl, C₂-C₁₁ heterocycloalkyl, C₂-C₁₁ heterocycloalkenyl, C₆-C₁₀aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkyl, C₆-C₁₀ heteroaralkyl, C₈-C₁₁aralkenyl or C₇-C₁₀ heteroaralkenyl, and alkyl, alkenyl, alkoxy,cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl,aryloxy, heteroaryl, heteroaryloxy, aralkyl, aralkyloxy, heteroaralkyl,aralkenyl and heteroaralkenyl in turn are unsubstituted or substitutedby one of the above-mentioned substituents; p is 0 or I and y is I and Zis a monovalent metal or y is ½ and Z is a divalent metal; or R₈ and R₉or R_(8′) and R_(9′) or R₈ and R₄₀ in the case of —NR₈R₉ or—NR_(8′)R_(9′), or R₈R₄₀N— together are tetramethylene, pentamethylene,—(CH₂)₂—O—(CH₂)₂—, —(CH₂)₂—S—(CH₂)₂—or —(CH₂)₂—NR₇—(CH₂)₂—, and R₇ is H,C₁-C₆ alkyl, C₇-C₁₁ aralkyl, C(O)R_(s2) or sulfonyl.

The sulfonyl substituent is, for example, of the formula R₁₀—SO₂— inwhich R₁₀ is C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, C₂-C₁₁ heterocycloalkyl,C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkyl or C₆-C₁₀ heteroaralkylwhich are unsubstituted or substituted by one or more substituentsselected from the group consisting of OH, halogen, C(O)OR_(s1),OC(O)R_(s4), C(O)R_(s2), nitro, NH₂, cyano, SO₃Z_(y), OSO₃Z_(y),NR₂OSO₃Z_(y), C₃-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₁-C₁₂ alkoxy, C₃-C₁₂cycloalkyl, C₃-C₁₂ cycloalkenyl, C₂-C₁₁ heterocycloalkyl, C₂-C₁₁heterocycloalkenyl, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy, C₅-C₉ heteroaryl, C₅-C₉heteroaryloxy, C₇-C₁₁ aralkyl, C₆-C₁₀ heteroaralkyl, C₈-C₁₁ aralkenyl,C₇-C₁₀ heteroaralkenyl, monoamino, diamino, sulfonyl, sulfonamide,carbamide, carbamate, sulfonhydrazide, carbohydrazide, carbohydroxamicacid residue and aminocarbonylamide, in which R_(s1) is hydrogen, Z_(y),C₁-C₁₂alkyl, C₂-C₁₂alkenyl, C₃-C₁₂ cycloalkyl, C₂-C₁₁ heterocycloalkyl,C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkyl or C₆-C₁₀ heteroaralkyl,R_(s4) is hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl,C₂-C₁₁ heterocycloalkyl, C₆-C₁₀ aryl, C₅-C₉ heteroaryl, C₇-C₁₁ aralkylor C₆-C₁₀ heteroaralkyl, and R₁₂ and R₂₀ are hydrogen, C₁-C₁₂ alkyl,C₂-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₃-C₁₂ cycloalkenyl, C₂-C₁₁heterocycloalkyl, C₂-C₁₁ heterocycloalkenyl, C₆-C₁₀ aryl, C₅-C₉heteroaryl, C₇-C₁₁ aralkyl, C₆-C₁₀ heteroaralkyl, C₈-C₁₁ aralkenyl orC₇-C₁₀ heteroaralkenyl, and alkyl, alkenyl, alkoxy, cycloalkyl,cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, aryloxy,heteroaryl, heteroaryloxy, aralkyl, heteroaralkyl, aralkenyl andheteroaralkenyl in turn are unsubstituted or substituted by one of theabove-mentioned substituents; and y is 1 and Z is a monovalent metal ory is ½ and Z is a divalent metal. Preferred neutral electron donorligands are derived, for example, from heteroarenes of the group

A more preferred group of compounds is formed when L² and L^(1′)independently of one another are pyridyl which is unsubstituted orsubstituted by one or more substituents from the group consisting ofC₁-C₁₂ alkyl, C₂-C₁₁ heterocycloalkyl, C₅-C₉ heteroaryl, halogen,monoamino, diamino and —C(O)H. Examples are

Another preferred group of compounds is formed when L² and L^(1′)together are bipyridyl, phenanthrolinyl, bithiazolyl, bipyrimidinyl orpicolylimine which are unsubstituted or substituted by one or moresubstituents from the group consisting of C₁-C₁₂ alkyl, C₆-C₁₀ aryl andcyano, the substituents alkyl and aryl being in turn unsubstituted orsubstituted by one or more substituents from the group consisting ofC₁-C₁₂ alkyl, nitro, monoamino, diamino and nitro- ordiamino-substituted —N═.N—C₆-C₁₀ aryl. Examples are:

Even more preferably, L² and L^(1′) are each independently selected fromthe group consisting of:

wherein R is selected from the group consisting of hydrogen or asubstituent selected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀alkenyloxy, C₂-C₂₀ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀alkylthio, C₁-C₂₀ alkylsulfonyl, C₁-C₂₀ alkylsulfinyl, and silyl.Optionally, the R group may be substituted with one or more moietiesselected from the group consisting of C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, andaryl which in turn may each be further substituted with one or moregroups selected from a halogen, a C₁-C₅ alkyl, C₁-C₅ alkoxy, and phenyl.Moreover, any of the heterocycles may further include one or morefunctional groups. Examples of suitable functional groups include butare not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester,ether, amine, imine, amide, nitro, carboxylic acid, disulfide,carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen,alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate,cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.Preferably R is selected from the group consisting of C₁-C₂₀ alkyl,aryl, ether, amine, halide, nitro, ester and pyridyl.

Preferably complexes 1-4 and 44-48 are used to make the preferredembodiments 5-29 and 49-83 of the inventive complex:

wherein sIMES or IMesH₂ is

Most preferably, L is an NHC, preferably an imidazolidine ligand, and L²and L^(1′) are pyridines.

The complexes can also be of the formulae:

wherein M and M′ are independently selected from the group consisting ofruthenium and osmium, X, X¹, L², L^(1′), R and R¹ are as previouslydefined, X′ and X^(1′) are substituted or unsubstituted and areindependently selected from the group from which X and X¹ are selected,R′ and R^(1′) are substituted or unsubstituted and are independentlyselected from the group from which R and R¹ are selected, L^(1″) isselected from the group from which L^(1′) is selected, L^(2′) is anybidentate, neutral electron donor ligand, and L³ is any tetradentate,neutral electron donor ligand.

The carbene complexes of the invention may also be cumulated. Forexample, one aspect of the invention is a catalyst of the generalstructure:

wherein M, L, L¹, L^(1′), L², X, X¹, R and R¹ are as defined above. Insuch cases, the starting complexes may be selected from the following:

Using cumulated pentacoordinated complexes, for example, those seen incomplexes 1-4 (a, b), in the inventive process will produce inventivecumulated hexacoordinated complexes. For example, the cumulatedcomplexes corresponding to complex 5 is as follows:

Similarly, compounds 6-29 may also have corresponding cumulatedcomplexes.

In all of the above carbene complexes, at least one of L, L¹, L^(1′),L², X, X¹, R and R¹, may be linked to at least one other of L, L¹,L^(1′), L², X, X¹, R and R¹ to form a bidentate or multidentate ligandarray.

Synthesis:

In general, the inventive catalysts are made by contacting excessneutral electron donor ligand, such as a pyridine, with the previouslydescribed penta-coordinated metal carbene catalyst complex of theformula:

wherein:

M, X, X¹, L, L¹, R and R¹ are as previously defined; and

wherein the third neutral electron donor ligand attaches to the metalcenter. Scheme 1 shows the general synthesis reaction for forming theinventive hexacoordinated metal carbene complexes:

wherein:

M, X, X¹, L, L¹, L^(1′), L², R and R¹ are as previously defined.

The synthesis of a preferred embodiment is shown in Scheme 2:

As shown by Schemes 1 and 2, in the presence of excess ligand L², thepentacoordinated complex loses the L¹ ligand and ligands L² and L^(1′)attach to the metal center. Ligands L² and L^(1′) may be the samecompound, for example, pyridines (when excess pyridine is used), or maytogether form a bidentate ligand. Alternatively, L¹ and L^(1′) may bethe same, in which case, the pentacoordinated compound does notnecessarily lose the L¹ ligand in the presence of excess L².

The inventive complex may also be a cumulated carbene complex of thegeneral formulas:

wherein M, X, X¹, L, L¹, L^(1′), L², R and R¹ are as previously defined.The synthesis of these compounds would follow Scheme 1 except that thestarting compound would be a pentacoordinated vinylidene orpentacoordinated cumulene, respectively. The synthesis of preferredembodiments of the vinylidenes can be seen in Scheme 3:

Other preferred compounds synthesized by the inventive method includewhere L² and L^(1′) form a bidentate ligand:

The inventive hexacoordinated catalyst complexes provide syntheticutility and utility in catalytic reactions. Without being bound bytheory, these complexes contain substitutionally labile ligands, forexample, pyridine and chloride ligands, and serve as a versatilestarting material for the synthesis of new ruthenium metal carbenecomplexes. The chloride ligands are more labile than in thecorresponding pentacoordinated phosphine-based complexes. As statedabove, X and X¹ are any anionic ligand. Preferably X and X¹ are selectedfrom the group consisting of chloride, bromide, iodide, Tp, alkoxide,amide, and thiolate. The pyridine ligands are more labile than thephosphines in the corresponding pentacoordinated phosphine-basedcomplexes. Again, as stated above, L, L¹, L^(1′), and L² can be anyneutral electron donor ligands, including a NHC ligand. Depending on thesize of the ligand, one or two neutral ligands (in addition to the NHC)may bind to the metal center.

Interestingly, the inventive catalyst complexes may be used in bothmetathesis reactions or the formation of an NHC ligand based complex. Asshown in Scheme 4, the hexacoordinated complex can lose a neutralelectron donor ligand to produce the pentacoordinated catalyst complex.The reaction may also proceed the other way to produce a hexacoordinatedcomplex in the presence of excess L².

The pentacoordinated complex may also lose the L¹ ligand to form themetathesis active tetracoordinated species (Scheme 5):

As shown in Scheme 5, the L¹ ligand may also attach to atetracoordinated species to form the pentacoordinated complex.

The tetracoordinated species may then initiate polymerization when inthe presence of an olefin, as shown in Scheme 6, or may form theNHC-ligand based pentacoordinated complex when in the presence of aprotected NHC-ligand (Scheme 7):

The following structure NHC-A-B indicates generally the protected formof a N-Heterocyclic Carbene (NHC).

It is also envisioned that the protected NHC-A-B may be of anunsaturated variety, such as

In the above structures, A is preferably H, Si, Sn, Li, Na, MgX³ andacyl, wherein X³ is any halogen, and B may be selected from the groupconsisting of CCl₃; CH₂SO₂Ph; C₆F₅; OR²¹; and N(R²²)(R²³), wherein R²¹is selected from the group consisting of Me, C₂H₅, i-C₃H₇, CH₂CMe₃,CMe₃, C₆H₁₁(cyclohexyl), CH₂Ph, CH₂norbornyl, CH₂norbornenyl, C₆H₅,2,4,6-(CH₃)₃C₆H₂ (mesityl), 2,6-i-Pr₂C₆H₂, 4-Me-C₆H₄ (tolyl), 4-C₁-C₆H₄;and wherein R²² and R²³ are independently selected from the groupconsisting of Me, C₂H₅, i-C₃H₇, CH₂CMe₃, CMe₃, C₆H₁₁ (cyclohexyl),CH₂Ph, CH₂norbornyl, CH₂norbornenyl, C₆H₅, 2,4,6-(CH₃)₃C₆H₂ (mesityl),2,6-i-Pr₂C₆H₂, 4-Me-C₆H₄ (tolyl), 4-C₁-C₆H₄). This approach relates tothe thermal generation of a NHC ligand from a stable (protected) NHCderivative with a release of a quantity of A-B. One of the morepreferred methods to generate a reactive NHC ligand is to employ astable carbene precursor where the A-B compound is also a reactive NHCligand. A detailed description of the protected NHC and related methodsof synthesis and use can be seen in U.S. patent application Ser. Nos.10/107,531 and 10/138,188 the contents of each of which are incorporatedherein by reference. The following structure for the sImesHCCl₃ shows apreferred embodiment of a protected NHC ligand for use with theinventive hexacoordinated complexes:

The NHC ligand based pentacoordinated complex may then lose the L ligandto form the metathesis active tetracoordinated species and proceed toinitiate the polymerization reaction in the presence of an olefin(Scheme 8):

It should also be noted that the hexacoordinated complex can undergo aligand exchange such that the NHC replaces another neutral electrondonor ligand resulting in an NHC ligand based hexacoordinated complex(Scheme 9):

In all the above schemes and complexes M, X, X¹, L, L¹, L^(1′), L², R,R¹, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, and R^(y) are as previously defined.

The reaction of complex 1 with a large excess (˜100 equiv) of pyridineresults in a rapid color change from red to bright green, and transferof the resulting solution to cold (−10° C.) pentane leads to theprecipitation of the bis-pyridine adduct (ImesH₂)(Cl)₂ (C₅H₅N)₂Ru═CHPh(31). Complex 31 can be purified by several washes with pentane and isisolated as an air-stable green solid that is soluble in CH₂Cl₂, benzeneand THF. This procedure provides complex 31 in 80-85% yield and iseasily carried out on a multigram scale.

Crystals suitable for X-ray crystal structure determination were grownby vapor diffusion of pentane into a saturated benzene solution of 31 atroom temperature. The collection and refinement parameters for thecrystallographic analysis are summarized in Table 1.

TABLE 1 Crystal Data and Structure Refinement for Complex 31 Empiricalformula C₇₆H₈₄Cl₄N₈Ru₂ Formula weight 1453.46 Crystal habit Rod Crystalsize 0.41 × 0.11 × 0.07 mm³ Crystal color Emerald green DiffractometerCCD area detector Wavelength 0.71073 Mo Kα Temperature 98 K Unit CellDimensions a = 12.3873(16) Å b = 15.529(2) Å c = 18.562(2) Å α =78.475(2)° β = 81.564(2)° γ = 76.745(2)° Volume 3386.2(8) Å³ Z 4 Crystalsystem Triclinic Space group P1 Density (calculated) 2.758 Mg/m³ θ range1.61-28.51° h min, max −16, 16 k min, max −20, 20 l min, max −24, 24Reflections collected 76469 Independent reflections 15655 GOF on F²1.438 R_(Int) 0.867 Final R indices [I > 2σ (I)] 0.0609 Final weighted R(F_(o) ²) 0.0855

A labeled view of complex 31 is shown in FIG. 1 and representative bondlengths and bond angles are reported in Table 2:

TABLE 2 Selected Bond Lengths (Å) and Angles (deg) for Complex 31 BondLengths (Å) Ru—C(1) 1.873(4) Ru—N(3) 2.203(3) Ru—Cl(1) 2.3995(12)Ru—C(38) 2.033(4) Ru—N(4) 2.372(4) Ru—Cl(2) 2.4227(12) Bond Angles (deg)C(38)—Ru—C(1) 93.61(17) C(38)—Ru—N(3) 176.40(14) C(38)—Ru—N(4)102.85(14) C(38)—Ru—Cl(1) 93.83(12) C(38)—Ru—Cl(2) 84.39(11)C(1)—Ru—N(3) 87.07(15) C(1)—Ru—N(4) 161.18(14) C(1)—Ru—Cl(1) 100.57(14)C(1)—Ru—Cl(2) 84.75(14) Cl(1)—Ru—Cl(2) 174.50(4)

Several structural isomers of the bis-pyridine adduct can be envisioned,but the solid-state structure reveals that the pyridines bind in a cisgeometry, occupying the coordination sites trans to the benzylidene andthe N-heterocyclic carbene ligand. The Ru═C(1) (benzylidene carbon) bondlength of 1.873(4) Å is slightly longer than those in five-coordinateruthenium olefin metathesis catalysts, including (Cl)₂(PCy₃)₂Ru═CHPh[d(Ru═C_(α))=1.838(2) Å] and complex 1 [d(Ru═C_(α))=1.835(2) Å]. Thelongated Ru═C_(α) bond in 31 likely results from the presence of atrans pyridine ligand. The Ru—C(38) (N-heterocyclic carbene) bond lengthof 2.033(4) Å is approximately 0.05 Å shorter than that in complex 1,which is likely due to the relatively small size and moderate transinfluence of pyridine relative to PCy₃. The 0.15 Å difference in theRu—C(1) and Ru—C(38) bond distances highlights the covalent nature ofthe former and the dative nature of the latter ruthenium-carbene bond.Interestingly, the two Ru—N bond distances differ by more than 0.15 Å,indicating that the benzylidene ligand exerts a significantly largertrans influence than the N-heterocyclic carbene.

The kinetics of the reaction between complex 1 and pyridine wasinvestigated in order to determine the mechanism of this ligandsubstitution. The reaction of complex 1 (0.88 M in toluene) with anexcess of pyridine-d₅ (0.18-0.69 M) is accompanied by a 150 nm red shiftvisible MLCT absorbance, and this transformation can be followed byUV-vis spectroscopy. The disappearance of starting material (502 nm) wasmonitored at 20° C., and in all cases, the data fit first-order kineticsover five half-lives. A plot of k_(obs) versus [C5D5N] is presented inFIG. 2. The data show an excellent linear fit (R²=0.999) even at highconcentrations of pyridine, and the y-intercept of this line (1.1×10⁻³)is very close to zero. The rate constant for phosphine dissociation(k_(B)) in complex 1 has been determined independently by ³¹Pmagnetization transfer experiments, and at 20° C., k_(B) is 4.1×10⁻⁵s⁻¹. This value of k_(B) places an upper limit on the rate ofdissociative ligand exchange in 1, and the observed rate constants forpyridine substitution are clearly 3 orders of magnitude larger thank_(B). Taken together, these results indicate that the substitution ofPCy₃ with pyridine proceeds by an associative mechanism with asecond-order rate constant of 5.7×10⁻² M⁻¹ s⁻¹ at 20° C. In markedcontrast, displacement of the phosphine ligand of 1 with olefinicsubstrates (which is the initiation event in olefin metathesisreactions) occurs via a dissociative mechanism.

Initial reactivity studies of complex 31 revealed that both pyridineligands are substitutionally labile. For example, benzylidene 31 reactsinstantaneously with 1.1 equiv. of PCy₃ to release pyridine andregenerate complex 1. This equilibrium can be driven back toward thepyridine adduct by addition of an excess of C₅D₅N, but it is readilyreestablished by removal of the volatiles under vacuum.

The facile reaction of 31 with PCy₃ suggested that the pyridines may bedisplaced by other incoming ligands and it was discovered that reactionof the bis-pyridine complex with a wide variety of phosphines provides asimple and divergent route to new ruthenium benzylidenes of the generalformula (ImesH₂)(PR₃)(Cl)₂Ru═CHPh. The combination of 31 and 1.1 equiv.of PR₃ results in a color change from green to red/brown and formationof the corresponding PR₃ adduct. The residual pyridine can be removedunder vacuum, and the ruthenium products are purified by several washeswith pentane and/or by column chromotography. This ligand substitutionworks well for a variety of alkyl- and aryl-substituted phosphinesincluding PPH₃, PBn₃, and P(n-Bu)₃ to produce complexes 32, 33 and 34.

Z=Ph (32) Z=(p-CF₃C₆H₄) (35)

Z=Bn (33) Z=(p-ClC₆H₄) (36)

Z=(n-Bu) (34) Z=(p-MeOC₆H₄) (37)

Additionally, the para-substituted triphenylphosphine derivatives 35, 36and 37 (containing para substituents CF₃, Cl, and OMe, respectively) canbe prepared using the inventive method. The synthetic accessibility ofcomplex 35 is particularly remarkable, because P(p-CF₃C₆H₄)₃ is anextremely electron-poor phosphine (χ=20.5 cm⁻¹). The triarylphosphineruthenium complexes 32, 35-37 are valuable catalysts as they are almost2 orders of magnitude more active for olefin metathesis reactions thanthe parent complex 1.

There appear to be both steric and electronic limitations on theincoming phosphine ligand in the pyridine substitution reaction. Forexample, complex 31 does not react with P(o-tolyl)₃ to produce a stableproduct, presumably due to the prohibitive size of the incoming ligand.The cone angle of P(o-tolyl)₃ is 194°, while that of PCy₃ (one of thelarger phosphines shown to successfully displace the pyridines of 31) is170°. Additionally, the electron-poor phosphine P(C₆F₆)₃ shows noreaction with 31, even under forcing conditions. This ligand has asignificantly lower electron donor capacity (χ=33.6 cm⁻¹) thanP(p-CF₃C₆H₄)₃ (χ=20.5 cm⁻¹) and also has a larger cone angle than PCy₃(θ=184°).

The methodology described herein represents a dramatic improvement overprevious synthetic routes to the complexes (NHC)(PR₃)(Cl)₂Ru═CHPh.Earlier preparations of these compounds involved reaction of thebis-phosphine precursor (PR₃)₂(Cl)₂Ru═CHPh with an NHC ligand. Thesetransformations were often low yielding (particularly when the NHC wassmall), and required the parallel synthesis of ruthenium precursorscontaining each PR₃ ligand. Furthermore, bis-phosphine startingmaterials containing PR₃ ligands that are smaller and lesselectron-donating than PPh₃ (θ=145; χ=13.25 cm⁻¹; pK_(a)=2.73) cannot beprepared, placing severe limitations on the complexes that are availableby the earlier preparation methods.

The chlorine ligands of 31 are also substantially labile relative tothose in the parent complex 1. For example, 31 reacts quantitativelywith NaI within 2 hours at room temperature to afford (ImesH₂)(I)₂(C₅H₅N)Ru═CHPh (38). In contrast, the reaction between 1 and NaI takesapproximately 8 hours to reach completion under identical conditions.Interestingly, ¹H NMR spectroscopy reveals that the diiodide complex 38contains only one pyridine ligand, while the analogous dichloridespecies 31 coordinates 2 equiv. of pyridine. The relatively large sizeof the iodide ligands and the lower electrophilicity at the metal centerin 38 (as compared to 31) are both believed to contribute to theformation of a five-coordinate complex in this system.

Complex 31 also reacts quantitatively with KTp[Tp=tris(pyrazolyl)borate] within 1 h at 25° C. to produce the brightgreen product Tp(ImesH₂)(Cl)Ru═CHPh (39), while the analogous reactionbetween complex 1 and KTp is extremely slow. (The latter proceeds toless than 50% completion even after several days at room temperature).Removal of the solvents under vacuum followed by filtration and severalwashes with pentane and methanol provides 39 as an air and moisturestable solid. Preliminary ¹H NMR studies also show that the combinationof 31 with an excess of KO^(t)-Bu produces the four-coordinatebenzylidene, (ImesH₂)—(O^(t)Bu)₂Ru═CHPh (40), quantitatively within 10min. at ambient temperature. In contrast, the reaction between 1 andKO^(t)-Bu to form 40 does not proceed to completion, even after severaldays at 35° C. Complex 40 may be considered a model for the 14-electronintermediate, (IMesH₂)(Cl)₂Ru═CHPh, involved in olefin metathesisreactions of 1.

The invention provides a high-yielding procedure for the preparation of(IMesH₂)(Cl)₂ (C₅H₅N)₂Ru═CHPh (31) from (IMesH₂)(Cl)₂ (PCy₃)Ru═CHPh (1).In contrast to the reaction of 1 with olefinic substrates, this ligandsubstitution proceeds by an associative mechanism. Complex 31 reactsreadily with phosphines, providing access to new complexes discussedherein. Complex 31 also undergoes reaction with KO^(t)-Bu, NaI, and KTpto provide new four-, five-, and six-coordinate ruthenium benzylidenes.The inventive methodology is useful for facilitating the development ofnew ruthenium olefin metathesis catalysts containing structurallydiverse ligand arrays.

Olefin Metathesis:

The inventive complexes are useful in olefin metathesis reactions,particularly for polymerization reactions. These catalysts can be usedin various metathesis reactions, including but not limited to,ring-opening metathesis polymerization of strained and unstrained cyclicolefins, ring-closing metathesis of acyclic dienes, acyclic dienemetathesis polymerization (“ADMET”), self- and cross-metathesisreactions, alkyne polymerization, carbonyl olefination, depolymerizationof unsaturated polymers, synthesis of telechelic polymers, and olefinsynthesis.

The most preferred olefin monomer for use in the invention issubstituted or unsubstituted dicyclopentadiene (DCPD). Various DCPDsuppliers and purities may be used such as Lyondell 108 (94.6% purity),Veliscol UHP (99+% purity), B. F. Goodrich Ultrene® (97% and 99%purities), and Hitachi (99+% purity). Other preferred olefin monomersinclude other cyclopentadiene oligomers including trimers, tetramers,pentamers, and the like; cyclooctadiene (COD; DuPont); cyclooctene (COE,Alfa Aesar); cyclohexenylnorbornene (Shell); norbornene (Aldrich);norbornene dicarboxylic anhydride (nadic anhydride); norbornadiene (ElfAtochem); and substituted norbornenes including butyl norbornene, hexylnorbornene, octyl norbornene, decyl norbornene, and the like.Preferably, the olefinic moieties include mono-or disubstituted olefinsand cycloolefins containing between 3 and 200 carbons. Most preferably,metathesis-active olefinic moieties include substituted or unsubstitutedcyclic or multicyclic olefins, for example, cyclopropenes, cyclobutenes,cycloheptenes, cyclooctenes, [2.2.1]bicycloheptenes,[2.2.2]bicyclooctenes, benzocyclobutenes, cyclopentenes, cyclopentadieneoligomers including trimers, tetramers, pentamers, and the like;cyclohexenes. It is also understood that such compositions includeframeworks in which one or more of the carbon atoms carry substituentsderived from radical fragments including halogens, pseudohalogens,alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino,aminoalkyl, and the like, or in which one or more carbon atoms have beenreplaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphorus,antimony, or boron. For example, the olefin may be substituted with oneor more groups such as thiol, thioether, ketone, aldehyde, ester, ether,amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate,phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide,carboalkoxy, carbamate, halogen, or pseudohalogen. Similarly, the olefinmay be substituted with one or more groups such as C₁-C₂₀ alkyl, aryl,acyl, C₁-C₂₀ alkoxide, aryloxide, C₃-C₂₀ alkyldiketonate,aryldiketonate, C₁-C₂₀ carboxylate, arylsulfonate, C₁-C₂₀alkylsulfonate, C₁-C₂₀ alkylthio, arylthio, C₁-C₂₀ alkylsulfonyl, andC₁-C₂₀ alkylsulfinyl, C₁-C₂₀ alkylphosphate, arylphosphate, wherein themoiety may be substituted or unsubstituted.

Examples of preferred polymerizable norbornene-type monomers include butare not limited to, norbornene (bicyclo[2.2.1]hept-2-ene),5-methyl-2-norbornene, ethylnorbornene, propylnorbornene,isopropylnorbornene, butylnorbornene, isobutylnorbornene,pentylnorbornene, hexylnorbornene, heptylnorbornene, octylnorbornene,decylnorbornene, dodecylnorbornene, octadecylnorbornene,p-tolylnorbornene, methylidene norbornene, phenylnorbornene,ethylidenenorbornene, vinylnorbornene, exo-dicyclopentadiene,endo-dicyclopentadiene, tetracyclododecene, methyltetracyclododecene,tetracyclododecadiene, dimethyltetracyclododecene,ethyltetracyclododecene, ethylidenyl tetracyclododecene,phenyltetracyclodecene, symmetrical and unsymmetrical trimers andtetramers of cyclopentadiene, 5,6-dimethylnorbornene,propenylnorbornene, 5,8-methylene-5a,8a-dihydrofluorene,cyclohexenylnorbornene, dimethanohexahydronaphthalene,endo,exo-5,6-dimethoxynorbornene, endo,endo-5,6-dimethoxynorbornene,2,3-dimethoxynorbornadiene,5,6-bis(chloromethyl)bicyclo[2.2.1]hept-2-ene,5-tris(ethoxy)silylnorbornene,2-dimethylsilylbicyclo[2.2.1]hepta-2,5-diene,2,3-bistrifluoromethylbicyclo[2.2.1]hepta-2,5-diene,5-fluoro-5-pentafluoroethyl-6-,6-bis(trifluoromethyl)bicyclo[2.2.1]hept-2-ene,5,6-difluoro-5-heptatafluoroisopropyl-6-trifluoromethyl)bicyclo[2.2.1]hept-2-ene,2,3,3,4,4,5,5,6-octafluorotricyclo[5.2.1.0]dec-8-ene, and5-trifluoromethylbicyclo[2.2.1]hept-2-ene, 5,6-dimethyl-2-norbornene,5-a-naphthyl-2-norbornene, 5,5-dimethyl-2-norbornene,1,4,4a,9,9a,10-hexahydro-9,10[1′,2′]-benzeno-1,4-methanoanthracene.indanylnorbornene (i.e., 1,4,4,9-tetrahydro-1,4-methanofluorene, thereaction product of CPD and indene),6,7,10,10-tetrahydro-7,10-methanofluoranthene (i.e., the reactionproduct of CPD with acenaphthalene),1,4,4,9,9,10-hexahydro-9,10[1′,2′]-benzeno-1,4-methanoanthracene,endo,endo-5,6-dimethyl-2-norbornene, endo,exo-5,6-dimethyl-2-norbornene,exo,exo-5,6-dimethyl-2-norbornene,1,4,4,5,6,9,10,13,14,14-decahydro-1,4-methanobenzocyclododecene (i.e.,reaction product of CPD and 1,5,9-cyclododecatriene),2,3,3,4,7,7-hexahydro-4,7-methano-1H-indene (i.e., reaction product ofCPD and cyclopentene), 1,4,4,5,6,7,8,8-octahydro-1,4-methanonaphthalene(i.e., reaction product of CPD and cyclohexene),1,4,4,5,6,7,8,9,10,10-decahydro-1,4-methanobenzocyclooctene (i.e.,reaction product of CPD and cyclooctene), and1,2,3,3,3,4,7,7,8,8,decahydro-4,7-methanocyclopent[a]indene.

These olefin monomers may be used alone or mixed with each other invarious combinations to adjust the properties of the olefin monomercomposition. For example, mixtures of cyclopentadiene dimer and trimersoffer a reduced melting point and yield cured olefin copolymers withincreased mechanical strength and stiffness relative to pure poly-DCPD.As another example, incorporation of COD, norbornene, or alkylnorbornene co-monomers tend to yield cured olefin copolymers that arerelatively soft and rubbery. The resulting polyolefin compositionsformed from the metathesis reactions are amenable to thermosetting andare tolerant of additives, stabilizers, rate modifiers, hardness and/ortoughness modifiers, fillers and fibers including, but not limited to,carbon, glass, aramid (e.g., Kevlar® and Twaron®), polyethylene (e.g.,Spectrao and Dyneemae®), polyparaphenylene benzobisoxazole (e.g.,Zylon®), polybenzamidazole (PBI), and hybrids thereof as well as otherpolymer fibers.

The metathesis reactions may optionally include formulation auxiliaries.Known auxiliaries include antistatics, antioxidants (primaryantioxidants, secondary antioxidants, or mixtures thereof), ceramics,light stabilizers, plasticizers, dyes, pigments, fillers, reinforcingfibers, lubricants, adhesion promoters, viscosity-increasing agents, anddemolding enhancers. Illustrative examples of fillers for improving theoptical physical, mechanical, and electrical properties include glassand quartz in the form of powders, beads, and fibers, metal andsemi-metal oxides, carbonates (e.g. MgCO₃, CaCO₃), dolomite, metalsulfates (e.g. gypsum and barite), natural and synthetic silicates (e.g.zeolites, wollastonite, and feldspars), carbon fibers, and plasticsfibers or powders.

The UV and oxidative resistance of the polyolefin compositions resultingfrom the metathesis reactions using the inventive carbene complex may beenhanced by the addition of various stabilizing additives such asprimary antioxidants (e.g., sterically hindered phenols and the like),secondary antioxidants (e.g., organophosphites, thioesters, and thelike), light stabilizers (e.g., hindered amine light stabilizers orHALS), and UV light absorbers (e.g., hydroxy benzophenone absorbers,hydroxyphenylbenzotriazole absorbers, and the like), as described inU.S. application Ser. No. 09/498,120, filed Feb. 4, 2000, the contentsof which are incorporated herein by reference.

Exemplary primary antioxidants include, for example, 4,4′-methylenebis(2,6-di-tertiary-butylphenol) (Ethanox 702®; Albemarle Corporation),1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene(Ethanox 330®; Albermarle Corporation),octadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate (Irganox1076®; Ciba-Geigy), and pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)(Irganox® 1010;Ciba-Geigy). Exemplary secondary antioxidants includetris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168; Ciba-Geigy),1:11(3,6,9-trioxaudecyl)bis(dodecylthio)propionate (Wingstay® 5N-1;Goodyear), and the like. Exemplary light stabilizers and absorbersincludebis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate(Tinuvin® 144 HALS; Ciba-Geigy),2-(2H-benzotriazol-2-yl)-4,6-Ditertpentylphenol (Tinuvin® 328 absorber;Ciba-Geigy), 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenyl(Tinuvin® 327 absorber; Ciba-Geigy), 2-hydroxy-4-(octyloxy)benzophenone(Chimassorb® 81 absorber; Ciba-Geigy), and the like.

In addition, a suitable rate modifier such as, for example,triphenylphosphine (TPP), tricyclopentylphosphine,tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites,triarylphosphites, mixed phosphites, or other Lewis base, as describedin U.S. Pat. No. 5,939,504 and U.S. application Ser. No. 09/130,586, thecontents of each of which are herein incorporated by reference, may beadded to the olefin monomer to retard or accelerate the rate ofpolymerization as required.

The resulting polyolefin compositions, and parts or articles ofmanufacture prepared therefrom, may be processed in a variety of waysincluding, for example, Reaction Injection Molding (RIM), Resin TransferMolding (RTM) and vacuum-assisted variants such as VARTM(Vacuum-Assisted RTM) and SCRIMP (Seemann Composite Resin InfusionMolding Process), open casting, rotational molding, centrifugal casting,filament winding, and mechanical machining. These processingcompositions are well known in the art. Various molding and processingtechniques are described, for example, in PCT Publication WO 97/20865,and U.S. Provisional Patent Application No. 60/360,755, filed Mar. 1,2002 and entitled “Polymer Processing Methods and Techniques UsingPentacoordinated or Hexacoordinated Ruthenium or Osmium MetathesisCatalysts,” the disclosures of which is incorporated herein byreference.

The metathesis reactions may occur in the presence or absence of asolvent. Examples of solvents that can be used in the polymerizationreaction include organic, protic, or aqueous solvents, which arepreferably inert under the polymerization conditions. Examples of suchsolvents include aromatic hydrocarbons, chlorinated hydrocarbons,ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof.Preferred solvents include benzene, toluene, p-xylene, methylenechloride, dichloroethane, dichlorobenzene, chlorobenzene,tetrahydrofuran, diethylether, pentane, methanol, ethanol, water ormixtures thereof. More preferably, the solvent is benzene, toluene,p-xylene, methylene chloride, dichloroethane, dichlorobenzene,chlorobenzene, tetrahydrofuran, diethylether, pentane, methanol,ethanol, or mixtures thereof. Most preferably, the solvent is toluene,or a mixture of benzene and methylene chloride. The solubility of thepolymer formed in the polymerization reaction will depend on the choiceof solvent and the molecular weight of the polymer obtained.

The inventive complexes have a well-defined ligand environment thatenables flexibility in modifying and fine-tuning the activity level,stability, solubility and ease of recovery of these catalysts. Thesolubility of the carbene compounds may be controlled by properselection of either hydrophobic or hydrophilic ligands as is well knownin the art. The desired solubility of the catalyst will largely bedetermined by the solubility of the reaction substrates and reactionproducts.

The inventive metal carbene complexes have shown a high rate ofinitiation allowing for most, if not all, of the complex added to thereaction to be consumed. Thus, less catalyst is wasted in the metathesisreaction. In contrast, the previous pentacoordinated initiators had ahigher amount of extractibles (i.e. unpolymerized monomer) remainingafter the reaction concluded. The rate of propogation is also slowed bythe presence of the two pyridine ligands. The high rate of initiationand low rate of propagation yields polymers with narrow polydisperitiesrelative to those achieved with the earlier pentacoordinated complexes.Moreover, it was determined that heat increases the rate of theinitiation. Thermal initiation of the pentacoordinated complexes can beseen in U.S. Pat. No. 6,107,420, the contents of which are incorporatedherein by reference. In general, the initiation and/or rate of themetathesis polymerization using the inventive catalysts is controlled bya method comprising contacting the inventive catalyst with an olefin andheating the reaction mixture. In a surprising and unexpected result, theT_(max) for the thermal initiation of the inventive catalyst issignificantly higher than the T_(max) for the previous pentacoordinatedcatalysts. Without being bound by theory, this is significant in that ina reaction using a metathesis catalyst, if the part or article beingprepared is a type of filled system (e.g., a system containingreinforcing fillers, fibers, beads, etc.), the filling material may actas a heat sink. With the previous pentacoordinated catalysts,post-curing was sometimes necessary due to the effect of the heat sinkresulting from a filled system. ROMP polymerization in the presence ofperoxide cross linking agents using pentacoordinated catalysts isdiscussed in U.S. Pat. No. 5,728,785, the contents of which areincorporated herein by reference. In contrast, the reactions using theinventive hexacoordinated catalysts generate significantly more internalheat. This high T_(max) reduces the need for post cure. Additionally,even if peroxides or radicals are added to promote crosslinking, thedegree of crosslinking in the part that uses the radical mechanism isincreased in comparison to a part prepared using the previouspentacoordinated metathesis catalysts. Moreover, the half-life isdependent on the maximum temperature. Using the inventive catalysts, thehalf life is reduced substantially, and therefore less catalyst isneeded, providing a significant commercial advantage. Without beingbound by theory, the higher T_(max) indicates that in a ROMP reaction,more rings are opened, and there is a better degree of cure. With ahigher T_(max), the extractibles are almost to zero, indicating thatalmost every molecule that can be reacted is reacted. For example, thevinylidenes are advantageous in that they are more stable at highertemperatures than the alkylidenes. When the protected NHC (e.g., asaturated Imes ligand as described in U.S. Provisional PatentApplication Nos. 60/288,680 and 60/278,311, the contents of each ofwhich are incorporated herein by reference), is added to the reactionmixture, a dramatic increase in peak exotherm is seen. Additionally, thetime to reach the peak is significantly reduced. A high peak exothermmeans more catalyst is available for polymerization, indicating that theextractibles are close to zero. Accordingly, the inventive catalystshave better conversion, better properties, even in the presence offillers and additives.

For the purposes of clarity, the specific details of the invention willbe illustrated with reference to especially preferred embodiments.However, it should be appreciated that these embodiments and examplesare for the purposes of illustration only and are not intended to limitthe scope of the invention.

EXAMPLES

General Procedures

Manipulation of organometallic compounds was performed using standardSchlenk techniques under an atmosphere of dry argon or in anitrogen-filled Vacuum Atmospheres drybox (O₂<2 ppm). NMR spectra wererecorded on a Varian Inova (499.85 MHz for ¹H; 202.34 MHz for ³¹P;125.69 MHz for ¹³C) or a Varian Mercury 300 (299.817 for ¹H; 121.39 MHzfor ³¹P; 74.45 MHz for ¹³C). ³¹P NMR spectra were referenced using H₃PO₄(ò=0 ppm) as an external standard. UV-vis spectra were recorded on an HP8452A diode-array spectrophotometer.

Materials and Methods

Pentane, toluene, benzene, and benzene-d₆ were dried by passage throughsolvent purification columns. Pyridine was dried by vacuum transfer fromCaH₂. All phosphines as well as KTp were obtained from commercialsources and used as received. Ruthenium complexes 1-4 and 44-48 wereprepared according to literature procedures.

Synthesis of (IMesH₂)(Cl₂H₈N₂)(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and1,10-phenanthroline (0.85 grams, 2 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstirred for approximately 12 hours at about 20° C. to about 25° C.during which time a color change from dark purple to brown-orange wasobserved. The reaction mixture was transferred into 75 mL of cold (about0° C.) pentane, and a brown-orange solid precipitated. The precipitatewas filtered, washed with 4×20 mL of cold pentane, and dried undervacuum to afford (IMesH₂)(C₁₂H₈N₂)(Cl)₂Ru═CHPh 5 as an brown-orangepowder (1.7 gram, 96% yield).

Synthesis of (IMesH₂)(C₅H₄BrN)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and3-bromopyridine (1.50 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to light green was observed. Thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane, and a light green solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford (IMesH₂)(C₅H₄BrN)₂(Cl)₂Ru═CHPh 6 as a light green powder (1.8grams, 86% yield).

Synthesis of (IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and4-pyrrolidinopyridine (1.40 grams, 4 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstirred for approximately 12 hours at about 20° C. to about 25° C.during which time a color change from dark purple to light green wasobserved. The reaction mixture was transferred into 75 mL of cold (about0° C.) pentane, and a light green solid precipitated. The precipitatewas filtered, washed with 4×20 mL of cold pentane, and dried undervacuum to afford (IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═CHPh 7 as a light greenpowder (1.9 gram, 93% yield).

¹H NMR (300 MHz, CD₂Cl₂): δ 19.05 (s, 1H, CHPh), 8.31 (d, 2H, pyridineCH, J_(HH)=6.6 Hz), 7.63 (d, 2H, ortho CH, J_(HH)=8.4 Hz), 7.49 (t, 1H,para CH, J_(HH)=7.4 Hz), 7.33 (d, 2H, pyridine CH, J_(HH)=6.9 Hz), 7.10(t, 2H, meta CH, J_(HH)=8.0 Hz), 7.03 (br. s, 2H, Mes CH), 6.78 (br. s,2H, Mes CH), 6.36 (d, 2H, pyridine CH, J_(HH)=6.3 Hz), 6.05 (d, 2H,pyridine CH, J_(HH)=6.9 Hz), 4.08 (br. d, 4H, NCH₂CH₂N), 3.30 (m, 4H,pyrrolidine CH₂), 3.19 (m, 4H, pyrrolidine CH₂), 2.61-2.22 (multiplepeaks, 18H, Mes CH₃), 2.02 (m, 4H, pyrrolidine CH₂), 1.94 (m, 4H,pyrrolidine CH₂).

Example: A 75 gram mass of DCPD (containing about 24% trimerized DCPD)was polymerized using (IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═CHPh=0.0151 grams at aDCPD:Ru ratio of (about 30,000:1) at a starting temperature of about24.2° C. Result: Time to reach maximum temperature (T_(max))=194seconds. T_(max)=208.9° C. Glass transition temperature measured bythermal mechanical analysis (TMA)=165° C. Percent residual monomer(toluene extraction at room temperature)=1.23%.

Synthesis of (IMesH₂)(C₆H₇N)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and4-methylpyridine (0.88 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to light green was observed. Thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane, and a light green solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford (IMesH₂)(C₆H₇N)₂(Cl)₂Ru═CHPh 8 as an light green powder (1.5grams, 84% yield).

Synthesis of (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and4,4′-bipyridine (0.74 grams, 2 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to brown-orange was observed. Thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane, and an brown-orange solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═CHPh 9 as a brown-orange powder (1.4gram, 71% yield).

¹H NMR (500 MHz, CD₂Cl₂): δ 19.15 (s, 1H, CHPh), 8.73-8.68 (multiplepeaks, 8H, pyridine CH), 7.63-6.77 (multiple peaks, 17H, pyridine CH,para CH, meta CH, Mes CH), 4.08 (br. d, 4H, NCH₂CH₂N), 2.61-2.24(multiple peaks, 18H, Mes CH₃).

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═CHPh=0.0153 grams at a DCPD:Ru ratio of (about30,000:1) at a starting temperature of about 24.2° C. Result: Time toreach maximum temperature (T_(max))=953 seconds. T_(max)=124.2° C.

Synthesis of (IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and4-dimethylaminopyridine (1.18 grams, 4 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstiffed for approximately 12 hours at about 20° C. to about 25° C.during which time a color change from dark purple to light green wasobserved. The reaction mixture was transferred into 75 mL of cold (about0° C.) pentane, and a light green solid precipitated. The precipitatewas filtered, washed with 4×20 mL of cold pentane, and dried undervacuum to afford (IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═CHPh 10 as a light greenpowder (1.9 gram, 99% yield).

¹H NMR (500 MHz, CD₂Cl₂): δ 19.10 (s, 1H, CHPh), 8.18 (d, 2H, pyridineCH, J_(HH)=6.5 Hz), 7.64 (d, 2H, ortho CH, J_(HH)=7.5 Hz), 7.48 (t, 1H,para CH, J_(HH)=7.0 Hz), 7.38 (d, 2H, pyridine CH, J_(HH)=6.5 Hz), 7.08(t, 2H, meta CH, J_(HH)=7.5 Hz), 7.00 (br. s, 2H, Mes CH) 6.77 (br. s,2H, Mes CH) 6.49 (d, 2H, pyridine CH, J_(HH)=6.0 Hz), 6.15 (d, 2H,pyridine CH, J_(HH)=7.0 Hz), 4.07 (br. d, 4H, NCH₂CH₂N), 2.98 (s, 6H,pyridine CH₃), 2.88 (s, 6H, pyridine CH₃), 2.61-2.21 (multiple peaks,18H, Mes CH₃).

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═CHPh=0.0141 grams at a DCPD:Ru ratio of (about30,000:1) at a starting temperature of about 24.2° C. Result: Time toreach maximum temperature (T_(max))=389 seconds. T_(max)=175.3° C.

Synthesis of (IMesH₂)(C₁₀H₈N₂)(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-bipyridine (0.74 grams, 2 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to brown-red was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and anbrown-red solid precipitated. The precipitate was filtered, washed with4×20 mL of cold pentane, and dried under vacuum to afford(IMesH₂)(C₁₀H₈N₂)(Cl)₂Ru═CHPh 11 as a brown-red powder (0.7 gram, 41%yield).

Synthesis of (IMesH₂)(C₆H₅NO)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and2-pyridinecarboxaldehyde (1.01 grams, 4 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstirred for approximately 12 hours at about 20° C. to about 25° C.during which time a color change from dark purple to dark blue wasobserved. The reaction mixture was transferred into 75 mL of cold (about0° C.) pentane, and a dark blue solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford (IMesH₂)(C₆H₅NO)₂(Cl)₂Ru═CHPh 12 as a dark blue powder (1.3 gram,70% yield).

Synthesis of (IMesH₂)(C₁₁H₉N)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.50 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to dark green was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and adark green solid precipitated. The precipitate was filtered, washed with4×20 mL of cold pentane, and dried under vacuum to afford(IMesH₂)(C₁₁H₉N)₂(Cl)₂Ru═CHPh 13 as a dark green powder (2.0 grams, 97%yield).

¹H NMR (500 MHz, CD₂Cl₂): δ 19.23 (s, 1H, CHPh), 8.74 (br. s, 2H,pyridine), 7.91 (br. s, 2H, pyridine), 7.70-7.08 (multiple peaks, 19H,ortho CH, para CH, meta CH, pyridine), 6.93 (br. S, 2H, Mes CH) 6.79(br. s, 2H, Mes CH), 4.05 (br. s, 4H, NCH₂CH₂N), 2.62-2.29 (multiplepeaks, 18H, Mes CH₃).

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(IMesH₂)(C₁₁H₉N)₂(Cl)₂Ru═CHPh=0.0153 grams at a DCPD:Ru ratio of (about30,000:1) at a starting temperature of about 13.4° C.

Result: Time to reach maximum temperature (T_(max))=145 seconds.T_(max)=202.2° C. Glass transition temperature measured by thermalmechanical analysis (TMA)=168° C. Percent residual monomer (tolueneextraction at room temperature)=1.17%.

Synthesis of (IMesH₂)(C₁₈H₁₂N₂)₂(Cl)₂Ru═CHPh

Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-biquinoline (1.21 grams, 2 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea slight color change from dark purple to brown-purple was observed. Thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane, and a brown-purple solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford (IMesH₂)(C₁₈H₁₂N₂)₂(Cl)₂Ru═CHPh 14 as a brown-purple powder (1.8gram, 93% yield).

Synthesis of (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CHPh

Complex 1 (1.1 g, 1.3 mmol) was dissolved in toluene, and pyridine (10mL) was added. The reaction was stirred for 10 min during which time acolor change from pink to bright green was observed. The reactionmixture was cannula transferred into 75 mL of cold (about 0° C.)pentane, and a green solid precipitated. The precipitate was filtered,washed with 4×20 mL of pentane, and dried under vacuum to afford(IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CHPh as a green powder (0.75 g, 80% yield).Samples for elemental analysis were prepared by recrystallization fromC₆ H₆/pentane followed by drying under vacuum. These samples analyze asthe monopyridine adduct (IMesH₂)(C₅H₅N)(Cl)₂Ru═CHPh, probably due toloss of pyridine under vacuum. ¹H NMR (C₆H₆): ∂ 19.67 (s, 1H, CHPh),8.84 (br. S, 2H, pyridine), 8.39 (br. s, 2H, pyridine), 8.07 (d, 2H,ortho CH, J_(HH)=8 Hz), 7.15 (t, 11H, para CH, J_(HH)=7 Hz), 6.83-6.04(br multiple peaks, 9H, pyridine, and Mes CH), 3.37 (br d, 4H, CH₂CH),2.79 (br s, 6H, Mes CH₃), 2.45 (br s, 6H, Mes CH₃), 2.04 (br s, 6H, MesCH₃). ¹³C{¹H}NMR(C₆D₆): ∂ 314.90 (m, Ru═CHPh), 219.10 (s, Ru—C(N)₂),152.94, 150.84, 139.92, 138.38, 136.87, 135.99, 134.97, 131.10, 130.11,129.88, 128.69, 123.38, 51.98, 51.37, 21.39, 20.96, 19.32. Anal. Calcdfor C₃₃H₃₇N₃Cl₂Ru: C, 61.20; H, 5.76; N, 6.49. Found: C, 61.25; H, 5.76;N, 6.58.

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CHPh=0.0127 grams at a DCPD:Ru ratio of (about30,000:1) at a starting temperature of about 12.1° C. Result: Time toreach maximum temperature (T_(max))=173 seconds. T_(max)=201.9° C. Glasstransition temperature measured by thermal mechanical analysis(TMA)=164° C. Percent residual monomer (toluene extraction at roomtemperature)=1.05%.

Polymerization Example: A 50 gram mass of hexylnorbornene waspolymerized using (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CHPh=0.0068 grams at aH_(x)N:Ru ratio of (about 30,000:1) at a starting temperature of about12.2° C.

Result: Time to reach maximum temperature (T_(max))=99 seconds.T_(max)=140.7° C.

Synthesis of (PCp₃)(C₁₂H₈N₂)(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 2 (2.0 grams) was dissolved in toluene (10 mL), and1,10-phenanthroline (1.01 grams, 2 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstirred for approximately 12 hours at about 20° C. to about 25° C.during which time a color change from dark purple to red-brown wasobserved. The reaction mixture was transferred into 75 mL of cold (about0° C.) pentane, and a red-brown solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford (PCp₃)(C₁₂H₈N₂)(Cl)₂Ru═CH—CH═C(CH₃)₂ 15 as an red-brown powder(1.8 gram, 98% yield).

Synthesis of (PCp₃)(C₅H₄BrN)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 2 (2.0 grams) was dissolved in toluene (10 mL), and3-bromopyridine (1.76 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to green was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and agreen solid precipitated. The precipitate was filtered, washed with 4×20mL of cold pentane, and dried under vacuum to afford(PCp₃)(C₅H₄BrN)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 16 as an green powder (0.2 gram,10% yield).

Synthesis of (PCp₃)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 2 (2.0 grams) was dissolved in toluene (10 mL), and pyridine(0.88 grams, 4 mol equivalents) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. during which time a color changefrom dark purple to green was observed. The reaction mixture wastransferred into 75 mL of cold (about 0° C.) pentane, and a green solidprecipitated. The precipitate was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCp₃)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 17 as a green powder (0.6 gram, 34%yield).

Synthesis of (PCp₃)(C₆H₇N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 2 (2.0 grams) was dissolved in toluene (10 mL), and4-methylpyridine (1.04 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to light green was observed. Thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane, and a light green solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford (PCp₃)(C₆H₇N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 18 as a light green powder(1.4 gram, 75% yield).

Synthesis of (PCy₃)(C₁₂H₈N₂)(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 3 (2.0 grams) was dissolved in toluene (10 mL), and1,10-phenanthroline (0.91 grams, 2 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstirred for approximately 12 hours at about 20° C. to about 25° C.during which time a color change from dark purple to orange-brown wasobserved. The reaction mixture was transferred into 75 mL of cold (about0° C.) pentane, and an orange-brown solid precipitated. The precipitatewas filtered, washed with 4×20 mL of cold pentane, and dried undervacuum to afford (PCy₃)(C₁₂H₈N₂)(Cl)₂Ru═CH—CH═C(CH₃)₂ 19 as anorange-brown powder (1.7 gram, 97% yield).

Synthesis of (PCy₃)(C₅H₄BrN)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 3 (2.0 grams) was dissolved in toluene (10 mL), and3-bromopyridine (1.58 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timeno dramatic color change from dark purple was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and apurple solid precipitated. The precipitate was filtered, washed with4×20 mL of cold pentane, and dried under vacuum to afford(PCy₃)(C₅H₄BrN)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 20 as a purple powder (1.4 gram,67% yield).

Synthesis of (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 3 (2.0 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.55 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to brown was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and abrown solid precipitated. The precipitate was filtered, washed with 4×20mL of cold pentane, and dried under vacuum to afford(PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 21 as a brown powder (1.6 gram, 77%yield).

Synthesis of (PCy₃)(C₆H₇N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 3 (2.0 grams) was dissolved in toluene (10 mL), and4-methylpyridine (0.93 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 12 hours at about 20° C. to about 25° C. during which timea color change from dark purple to green was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and agreen solid precipitated. The precipitate was filtered, washed with 4×20mL of cold pentane, and dried under vacuum to afford(PCy₃)(C₆H₇N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 22 as a green powder (1.6 gram, 91%yield).

Synthesis of (PCy₃)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 3 (2.0 grams) was dissolved in toluene (10 mL), and pyridine(0.79 grams, 4 mol equivalents) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. during which time a color changefrom dark purple to light green was observed. The reaction mixture wastransferred into 75 mL of cold (about 0° C.) pentane, and a light greensolid precipitated. The precipitate was filtered, washed with 4×20 mL ofcold pentane, and dried under vacuum to afford(PCy₃)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 23 as a light green powder (1.4gram, 83% yield).

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(PCy₃)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂=0.0237 grams at a DCPD:Ru ratio of(about 15,000:1) at a starting temperature of about 52.2° C.

Result: Time to reach maximum temperature (T_(max))=1166 seconds.T_(max)=60.2° C.

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(PCy₃)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂=0.0237 grams in the presence ofsImesHCCl₃=0.0297 grams at a DCPD:Ru:sImesHCCl₃ ratio of (about15,000:1:2) at a starting temperature of about 49.4° C. Result: Time toreach maximum temperature (T_(max))=715 seconds. T_(max)=173.3° C.

Synthesis of (IMesH₂)(CI H₉N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 4 (1.5 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.13 grams, 4 mol equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 2 hours at about 20° C. to about 25° C. during which timea color change from brown to green was observed. The reaction mixturewas transferred into 75 mL of cold (about 0° C.) pentane, and a greensolid precipitated. The precipitate was filtered, washed with 4×20 mL ofcold pentane, and dried under vacuum to afford(IMesH₂)(C₁₁H₉N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 24 as a green powder (0.9 gram,58% yield). Synthesis of (IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 4 (1.5 grams) was dissolved in toluene (10 mL), and4-pyrrolidinopyridine (1.08 grams, 4 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstirred for approximately 2 hours at about 20° C. to about 25° C. duringwhich time a color change from brown to green was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and agreen solid precipitated. The precipitate was filtered, washed with 4×20mL of cold pentane, and dried under vacuum to afford(IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 25 as a green powder (1.0 gram,65% yield).

¹H NMR (300 MHz, CD₂Cl₂): δ 19.05 (d, 1H, CH—CH═C(CH₃)₂, J_(HH)=11 Hz),8.14 (br. S, 2H, pyridine CH), 7.69 (d, 1H, CH—CH═C(CH₃)₂, J_(HH)=11Hz), 7.36 (d, 2H, pyridine CH, J_(HH)=6.0 Hz), 7.04 (s, 2H, Mes CH),6.81 (s, 2H, Mes CH), 6.36 (br. s, 2H, pyridine CH), 6.12 (d, 2H,pyridine CH, J_(HH)=6.0 Hz), 4.06 (m. d, 4H, NCH₂CH₂N), 3.29 (br. s, 4H,pyrrolidine CH₂), 3.23 (br. s, 4H, pyrrolidine CH₂), 2.55-2.12 (multiplepeaks, 18H, Mes CH₃), 2.02 (br. s, 4H, pyrrolidine CH₂), 1.97 (br. s,4H, pyrrolidine CH₂), 1.10 (s, 3H, CH—CH═C(CH₃)₂), 1.08 (s, 3H,CH—CH═C(CH₃)₂).

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂=0.0147 grams at a DCPD:Ru ratioof (about 30,000:1) at a starting temperature of about 24.7° C.

Result: Time to reach maximum temperature (T_(max))=181 seconds.T_(max)=200.9° C. Glass transition temperature measured by thermalmechanical analysis (TMA)=144° C. Percent residual monomer (tolueneextraction at room temperature)=3.93%.

Synthesis of (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 4 (1.5 grams) was dissolved in toluene (10 mL), and4,4′-bipyridine (0.57 grams, 2 mot equivalents) was added. The reactionflask was purged with argon and the reaction mixture was stirred forapproximately 2 hours at about 20° C. to about 25° C. during which timeno dramatic color change from brown was observed. The reaction mixturewas transferred into 75 mL of cold (about 0° C.) pentane, and a brownsolid precipitated. The precipitate was filtered, washed with 4×20 mL ofcold pentane, and dried under vacuum to afford(IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 26 as a brown powder (1.0 gram,64% yield).

Synthesis of (IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 4 (1.5 grams) was dissolved in toluene (10 mL), and4-dimethylaminopyridine (0.89 grams, 4 mol equivalents) was added. Thereaction flask was purged with argon and the reaction mixture wasstirred for approximately 2 hours at about 20° C. to about 25° C. duringwhich time a color change from brown to green was observed. The reactionmixture was transferred into 75 mL of cold (about 0° C.) pentane, and agreen solid precipitated. The precipitate was filtered, washed with 4×20mL of cold pentane, and dried under vacuum to afford(IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ 27 as a green powder (0.9 gram,63% yield).

¹H NMR (500 MHz, CD₂Cl₂): δ 19.10 (d, 111, CH—CH═C(CH₃)₂, J_(HH)=11.5Hz,), 8.18 (br. s, 2H, pyridine CH), 7.69 (d, 1H, CH—CH═C(CH₃)₂,J_(HH)=11.5 Hz), 7.41 (br. s, 2H, Mes CH), 6.49 (br. s, 2H, pyridineCH), 6.24 (br. s, 2H, Mes CH), 4.06 (br. m, 4H, NCH₂CH₂N), 2.99 (s, 6H,pyridine CH₃), 2.59 (s, 6H, pyridine CH₃), 2.36-2.12 (multiple peaks,18H, Mes CH₃), 1.07 (s, 3H, CH—CH═C(CH₃)₂), 1.06 (s, 3H, CH—CH═C(CH₃)₂).

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂=0.0138 grams at a DCPD:Ru ratioof (about 30,000:1) at a starting temperature of about 24.2° C.

Result: Time to reach maximum temperature (T_(max))=200 seconds.T_(max)=200.9° C. Glass transition temperature measured by thermalmechanical analysis (TMA)=145° C. Percent residual monomer (tolueneextraction at room temperature)=4.57%.

Polymerization Example: A 50 gram mass of hexylnorbornene waspolymerized using (IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂=0.0074 gramsat a H₁₁N:Ru ratio of (about 30,000:1) at a starting temperature ofabout 16.2° C.

Result: Time to reach maximum temperature (T_(max))=182 seconds.T_(max)=141.7° C.

Synthesis of (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

Complex 4 (0.5 grams) was dissolved in toluene (10 mL), and pyridine (10mL) was added. The reaction flask was purged with argon and the reactionmixture was stirred for approximately 12 hours at about 20° C. to about25° C. during which time a color change from brown to brown-green wasobserved. The reaction mixture was transferred into 75 mL of cold (about0° C.) pentane, and a green solid precipitated. The precipitate wasfiltered, washed with 4×20 mL of cold pentane, and dried under vacuum toafford 28 (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂ as green crystals (0.2gram, 47% yield).

¹H NMR (300 MHz, CD₂Cl₂): δ 19.19 (d, 11H, Ru═CH—CH═C(CH₃)₂, J_(HH)=10.8Hz), 8.60-6.85 (multiple peaks, 15H, pyridine, Mes CH, Ru═CH—CH═C(CH₃)₂,4.07 (m, 4H, NCH₂CH₂N), 2.58-2.27 (multiple peaks, 12H, Mes CH₃), 2.31(s, 3H, Mes CH₃), 2.19 (s, 3H, Mes CH₃), 1.09 (s, 3H, CH—CH═C(CH₃)₂),1.08 (s, 3H, CH—CH═C(CH₃)₂).

Polymerization Example: A 75 gram mass of DCPD (containing about 24%trimerized DCPD) was polymerized using(IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂=0.0123 grams at a DCPD:Ru ratio of(about 30,000:1) at a starting temperature of about 12.5° C.

Result: Time to reach maximum temperature (T_(max))=129 seconds.T_(max)=197.1° C. Glass transition temperature measured by thermalmechanical analysis (TMA)=157° C. Percent residual monomer (tolueneextraction at room temperature)=2.13%.

Synthesis of (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═CHPh (31)

Complex 1 (4.0 g, 4.7 mmol) was dissolved in toluene (10 mL), andpyridine (30 mL, 0.37 mol) was added. The reaction was stirred for 10min during which time a color change from red to bright green wasobserved. The reaction mixture was cannula transferred into 100 mL ofcold (−10° C.) pentane, and a green solid precipitated. The precipitatewas filtered, washed with 4×50 mL of pentane, and dried under vacuum toafford 31 as a green powder (2.9 g, 85% yield). Samples for elementalanalysis were prepared by recrystallization from C₆H₆/pentane followedby drying under vacuum. These samples analyze as the monopyridine adduct(IMesH₂)(C₅H₅N)(Cl)₂Ru═CHPh, probably due to loss of pyridine undervacuum. ¹H NMR (C₆D₆): δ 19.67 (s, 1H, CHPh), 8.84 (br. s, 2H,pyridine), 8.39 (br. s, 2H, pyrdine), 8.07 (d, 2H, ortho CH, J_(HH)=8Hz), 7.15 (t, 11H, para CH, J_(HH)=7 Hz), 6.83-6.04 (br. multiple peaks,9H, pyridine, Mes CH), 3.37 (br. d, 4H, CH₂CH₂), 2.79 (br. s, 6H, MesCH₃), 2.45 (br. s, 6H, Mes CH₃), 2.04 (br. s, 6H, Mes CH₃). C{¹H} NMR(C₆D₆): δ 314.90 (m, Ru═CHPh), 219.10 (s, Ru—C(N)₂), 152.94, 150.84,139.92, 138.38, 136.87, 135.99, 134.97, 131.10, 130.11, 129.88, 128.69,123.38, 51.98, 51.37, 21.39, 20.96, 19.32. Anal. Calcd forC₃₃H₃₇N₃Cl₂Ru: C, 61.20; H, 5.76; N, 6.49. Found: C, 61.25; H, 5.76; N,6.58.

Represententative Synthesis of a Phosphine Complex:IMesH₂)(PPh₃)(Cl)₂Ru═CHPh (41)

Complex 31 (150 mg, 0.21 mmol) and PPh₃ (76 mg, 0.28 mmol) were combinedin benzene (10 mL) and stirred for 10 min. The solvent was removed undervacuum, and the resulting brown residue was washed with 4×20 mL ofpentane and dried in vacuo. Complex 41 was obtained as a brownish powder(125 mg, 73% yield). ³¹P{¹H} NMR (C₆D₆): δ 37.7 (s). ¹H NMR (C₇D₈): δ19.60 (s, ¹H, Ru═CHPh), 7.70 (d, 2H, ortho CH, J_(HH)=8 Hz), 7.29-6.71(multiple peaks, 20H, PPh₃, para CH, meta CH, and Mes CH), 6.27 (s, 2H,Mes CH), 3.39 (m, 4H, CH₂CH₂), 2.74 (s, 6H, ortho CH₃), 2.34 (s, 6H,ortho CH₃), 2.23 (s, 3H, para CH₃), 1.91 (s, 3H, para CH₃). ¹³C{¹H} NMR(C₆D₆): δ 305.34 (m, Ru—CHPh), 219.57 (d, Ru—C(N)₂, J_(CP)=92 Hz),151.69 (d, J_(CP)=4 Hz), 139.68, 138.35,138.10, 138.97, 137.78, 135.89135.21, 135.13, 131.96, 131.65, 131.36, 130.47, 129.83, 129.59 (d,J_(CP)=2 Hz), 129.15, 128.92, 128.68, 128.00, 52.11 (d, J_(CP)=4 Hz),51.44 (d, J_(CP)=2 Hz), 21.67, 21.35, 21.04, 19.21. Anal. Calcd forC₄₆H₄₇N₂Cl₂PRu: C, 66.50; H, 5.70; N, 3.37. Found: C, 66.82; H, 5.76; N,3.29.

Synthesis of (IMesH₂)(O'BU)₂Ru═CHPh (42)

Complex 31 (7.5 mg, 0.010 mmol) and KO'Bu (3 mg, 0.027 mmol) werecombined in C₆D₆ (0.6 mL) in an NMR tube under nitrogen. The reactionmixture was allowed to stand for 15-20 min, during which time a colorchange from green to dark red was was observed, and NMR spectra wererecorded after 30 min. ¹H NMR (C₆D₆): δ 16.56 (s, 1H, Ru═CHPh), 7.63 (d,2H, ortho CH, J_(HH)=7 Hz), 7.2-7.1 (multiple peaks, 3H, meta CH andortho CH), 6.97 (s, 4H, Mes CH), 3.43 (s, 4H CH₂CH₂), 2.59 (s, 12H,ortho CH₃), 2.29 (s, 6H, para CH₃), 1.18 (s, 18H, Bu).

Synthesis of Tp(IMesH₂)(Cl)Ru═CHPh (43)

KTp (87 mg, 0.34 mmol) and complex 31 (125 mg, 0.17 mmol) were combinedin CH₂Cl₂ (10 mL) and stirred for 1 hour. Pentane (20 mL) was added toprecipitate the salts, and the reaction was stirred for an additional 30min and then cannula filtered. The resulting bright green solution wasconcentrated, and the solid residue was washed with pentane (2×10 mL)and methanol (2×10 mL) and dried under vacuum to afford 43 (84 mg, 66%yield) as an analytically pure green powder. ¹H NMR (CD₂Cl₂): δ 18.73(s, 1H, Ru═CHPh), 7.87 (d, 1H, Tp, J_(HH)=2.4 Hz), 7.41 (d, 1H, Tp,J_(HH)=2.1 Hz), 7.35-7.30 (multiple peaks, 3H, Tp and para CH), 7.08 (d,1 h, Tp, J_(HH)=1.5 Hz), 6.82 (br. s, 5H, Mes CH, ortho CH and meta CH),6.24 (br. s, 3H, Mes CH), 6.16 (t, 1H, Tp, J_(HH)=1.8 Hz) 5.95 (d, 1H,Tp, J_(HH)=1.5 Hz), 5.69 (t, 1H, Tp, J_(HH)=2.4 Hz), 5.50 (t, 1H, Tp,J_(HH)=1.8 Hz), 3.77 (br. d, 4H, CH₂CH₂), 2.91-0.893 (br. multiplepeaks, 18H, ortho CH₃, para CH₃). ¹³C{¹H} (CD₂Cl₂): δ 324.29 (m,Ru═CHPh), 220.57 (s, Ru—C(N)₂), 151.50, 146.08, 145.39, 142.07, 137.94,136.57, 134.41, 133.18, 130.60 (br), 129.55, 127.98, 106.41, 105.19,104.51, 53.77 (br), 21.26, 20.32 (br). Anal. Calcd for C₃₇H₄₂N₈C1BRu: C,59.56; H, 5.67; N, 15.02. Found: C, 59.20; H, 5.67; N, 14.72.

Kinetics of the Reaction of 1 with C₅D₅N

In a cuvette fitted with a rubber septum, a solution of 1 (0.88 mM) intoluene (1.6 mL) was prepared. This solution was allowed to thermallyequilibrate in the UV-vis spectrometer at 20° C. Neat pyridine-d₅(25-100 μL) was added via microsyringe, and the reaction kinetics wasfollowed by monitoring the disappearance of starting material (502 nm).For each run, the data were collected over 5 half-lives and were fittedto a first-order expoential. Typical R² values for the exponential curvefits were greater than 0.999.

X-ray Crystal Structure of 31

Crystal, intensity collection, and refinement details were summarized inTable 1. The selected crystal was mounted on a glass fiber withParatone-N oil and transferred to a Bruker SMART 1000 CCD area detectorequipped with a Crystal Logic CL24 low-temperature device. Data werecollected with ω-scans at seven φ values and subsequently processed withSAINT. No absorption or decay corrections were applied. SHELXTL was usedto solve (by direct methods and subsequent difference Fourier maps) andto refine (full-matrix least-squares on 12),the structure. There are twomolecules in the asymmetric unit. All non-hydrogen atoms were refinedanisotropically; the hydrogen atoms were placed at calculated positionswith U_(iSO) values based on the U_(eq) of the attached atom. Pertinentbond lengths and angles for one molecule are presented in Table 2.

Synthesis of (IMes)(C₅H₅N)₂(Cl)₂Ru═CHPh

In a nitrogen filled glovebox, 0.120 g (0.142 mmol) of(IMes)(PCy₃)Cl₂Ru═CHPh were dissolved in 1 mL of pyridine (largeexcess). The solution, which turned green immediately, was stirred atroom temperature for 30 minutes. Then 20 mL of hexanes was added, andthe flask was stored at −10° C. overnight. The supernatant was decantedfrom the green precipitate. The precipitate was washed twice with 20 mLhexanes and dried under vacuum to obtain 0.080 g (78% yield) of thebright green product (IMes)(py)₂Cl₂Ru═CHPh.

¹H NMR (499.852 MHz, CD₂Cl₂): δ 19.41 (s, 1H, CHPh), 8.74 (d, 2H, J=7.5Hz), 7.96 (d, 2H, J=8.5 Hz), 7.70 (d, 2H, J=12.5 Hz), 7.55 (t, 1H,J=12.5 Hz), 7.44 (t, 1H, J=12 Hz), 7.33 (t, 1H, J=12 Hz), 7.06 (m, 3H),7.05 (s, 2H), 6.83 (m, 1H), 6.79 (s, 6H), 2.28 (s, 6H, para CH₃ on Mes),2.22 (br s, 12H, ortho CH₃ on Mes).

Characterization of (PCy₃)(C₅H₅N)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

¹H NMR (499.852 MHz, C₆D₆): δ 20.18 (overlapping dd, 1H, J=10.3 Hz,Ru═CH), 9.14 (br s, 4H, pyridine), 8.07 (d, 1H, J=11.5 Hz, —CH═), 6.68(br s, 3H, pyridine), 6.43 (br m, 3H, pyridine), 2.54 (qt, 3H, J=11.5Hz, PCy₃), 2.27 (d, 6H, J=11.5 Hz, PCy₃), 1.91 (qt, 6H, J=12 Hz, PCy₃),1.78 (d, 6H, J=10.5 Hz, PCy₃), 1.62 (m, 4H, PCy₃), 1.26 (s, 3H, CH₃),1.23 (m, 8H, PCy₃), 0.75 (s, 3H, CH₃). ³¹P{¹H} NMR (121.392 MHz, C₆D₆):δ 37.17 (s).

Observation of (Ph₃Tri)(C₇H₁₀N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂

0.020 g of (Ph₃Tri)(PCy₃)(Cl)₂Ru═CH—CH═C(CH₃)₂, 0.020 g of4-dimethylaminopyridine (excess), and 0.060 mL of CD₂Cl₂ were added to ascrew-cap NMR tube. The ¹H NMR spectrum after 2 hours at roomtemperature showed complete conversion to the desired product(Ph₃Tri)(C₇H₁₀N₂)₂(Cl)₂Ru═CH—CH═C(CH₃)₂.

¹H NMR (499.852 MHz, C₆D₆): δ 18.57 (d, 1H, J=13 Hz, Ru═CH), 8.53 (d,J=8 Hz), 7.84 (d, J=6.5 Hz), 7.73-6.84 (multiplets), 6.26 (d, J=7 Hz),6.09 (m), 6.04 (d, J=10.5 Hz), 6.01 (d, J=10.5 Hz), 5.42 (d, J=10.5 Hz),5.38 (d, J=17.5 Hz), 3.22 (s), 3.01 (s), 2.99 (s), 1.73 (s), 1.23 (s).

Synthesis of (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and pyridine(0.9 grams) was added. The reaction flask was purged with argon and thereaction mixture was stirred for approximately 12 hours at about 20° C.to about 25° C. After approximately 12 hours the reaction mixture wastransferred into 75 mL of cold (about 0° C.) pentane. The pentanemixture was filtered, washed with 4×20 mL of cold pentane, and driedunder vacuum to afford (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CHPh 49 as an orangepowder (1.5 gram, 88% yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CHPh=0.0379 grams at a DCPD:Ruratio of (about 10,000:1) at a starting temperature of about 81.3° C.Result: Time to reach maximum temperature (T_(max))=97 seconds.T_(max)=169.1° C.

Example (2)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CHPh=0.0377 grams in thepresence of sIMesHCCl₃=0.0450 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 88.2° C. Result:Time to reach maximum temperature (T_(max))=205 seconds. T_(max)=249.7°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=164.77° C.

Synthesis of (PCy₃)(C₉H₁₂N₂)₂(Cl)₂Ru═C═CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and4-pyrrolidinopyridine (1.5 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford (PCy₃)(C₉H₁₂N₂)₂(Cl)₂Ru═C═CHPh50 as a light brown powder (1.9 gram, 95% yield).

Synthesis of (PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and4-dimethylaminopyridine (1.3 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford (PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CHPh51 as an orange powder (1.8 gram, 95% yield).

Synthesis of (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.2 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CHPh52 as an orange powder (0.9 gram, 43% yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CHPh=0.0455 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about79.4° C. Result: Time to reach maximum temperature (T_(max))=90 seconds.T_(max)=170.2° C.

Example (2)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CHPh=0.0451 grams in thepresence of sIMesHCCl₃=0.0450 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 82.9° C. Result:Time to reach maximum temperature (T_(max))=148 seconds. T_(max)=242.1°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=158.28° C.

Example (3)

A 75 g mass of hexylnorbornene was polymerized using(PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CHPh=0.0244 g at a H_(x)N:Ru reactant ratio of(15,000:1) at a starting temperature of about 80.1° C. Result: Time toreach maximum temperature (T_(max))=391 seconds. T_(max)=155.4° C.

Example (4)

A 75 g mass of hexylnorbornene, was polymerized using(PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CHPh=0.0246 g in the presence ofs-ImesHCCl₃=0.0240 g at a H_(x)N:Ru:s-ImesHCCl₃ reactant ratio of(15,000:1:2) at a starting temperature of about 81.7° C. Result: Time toreach maximum temperature (T_(max))=224 seconds. T_(max)=193.9° C.

Example (5)

A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g ofDCPD (containing 24 wt % trimerized DCPD) and 37.5 g of hexylnorbornene,was polymerized using (PCy₃)(Cl H₉N)₂(Cl)₂Ru═C═CHPh=0.0276 g at aDCPD:Ru reactant ratio of (15,000:1) and H_(x)N:Ru reactant ratio of(15,000:1), by heating the mixture to a starting temperature of about80.1° C. Result: Time to reach maximum temperature (T_(max))=195seconds. T_(max)=148.8° C.

Example (6)

A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g ofDCPD (containing 24 wt % trimerized DCPD) and 37.5 g of hexylnorbornene,was polymerized using (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CHPh=0.0275 g in thepresence of s-ImesHCCl₃=0.0269 g at a DCPD:Ru:s-ImesHCCl₃ reactant ratioof (15,000:1:2) and H_(x)N:Ru:s-ImesHCCl₃ reactant ratio of(15,000:1:2), by heating the mixture to a starting temperature of about82.1° C. Result: Time to reach maximum temperature (T_(max))=180seconds. T_(max)=217.3° C.

Synthesis of (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 45 (2.0 grams) was dissolved in toluene (10 mL), and pyridine(0.9 grams) was added. The reaction flask was purged with argon and thereaction mixture was stirred for approximately 12 hours at about 20° C.to about 25° C. After approximately 12 hours the reaction mixture wastransferred into 75 mL of cold (about 0° C.) pentane. The pentanemixture was filtered, washed with 4×20 mL of cold pentane, and driedunder vacuum to afford (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 53 as anorange powder (1.5 gram, 88% yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0370 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about79.5° C. Result: Time to reach maximum temperature (T_(max))=155seconds. T_(max)=207.4° C. Glass transition temperature measured bythermal mechanical analysis (TMA)=70.73° C.

Example (2)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0368 grams in thepresence of sIMesHCCl₃=0.0446 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 82.2° C. Result:Time to reach maximum temperature (T_(max))=76 seconds. T_(max)=239.7°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=178.83° C.

Example (3)

A 75 g mass of hexylnorbornene was polymerized using(PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0148 g at a H_(x)N:Ru reactantratio of (20,000:1) at a starting temperature of about 82.4° C. Result:Time to reach maximum temperature (T_(max))=212 seconds. T_(max)=189.4°C.

Example (4)

A 75 g mass of hexylnorbornene, was polymerized using(PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0149 g in the presence ofs-ImesHCCl₃=0.0092 g at a H_(x)N:Ru:s-ImesHCCl₃ reactant ratio of(20,000:1:1) at a starting temperature of 80.9° C. Result: Time to reachmaximum temperature (T_(max))=154 seconds. T_(max)=194.5° C.

Example (5)

A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g ofDCPD (containing 24 wt % trimerized DCPD) and 37.5 g of hexylnorbornene,was polymerized using (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0163 g at aDCPD:Ru reactant ratio of (20,000:1) and H₁₁N:Ru reactant ratio of(20,000:1), by heating the mixture to a starting temperature of about82.3° C. Result: Time to reach maximum temperature (T_(max))=149seconds. T_(max)=191.5° C.

Example (6)

A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g ofDCPD (containing 24 wt % trimerized DCPD) and 37.5 g of hexylnorbornene,was polymerized using (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0163 g in thepresence of s-ImesHCCl₃=0.0100 g at a DCPD:Ru:s-ImesHCCl₃ reactant ratioof (20,000:1:2) and H_(x)N:Ru:s-ImesHCCl₃ reactant ratio of(20,000:1:2), by heating the mixture to a starting temperature of about81.2° C. Result: Time to reach maximum temperature (T_(max))=169seconds. T_(max)=221.3° C.

Synthesis of (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and4,4′-bipyridine (1.5 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CHPh54 as an orange powder (1.9 gram, 90% yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CHPh=0.0457 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about82.7° C. Result: Time to reach maximum temperature (T_(max))=246seconds. T_(max)=159.9° C.

Example (2)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CHPh=0.0462 grams in thepresence of sIMesHCCl₃=0.0448 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 82.3° C. Result:Time to reach maximum temperature (T_(max))=244 seconds. T_(max)=230.0°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=126.338° C.

Synthesis of (PCy₃)(C₁₂H₈N₂)(Cl)₂Ru═C═CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and1,10-phenanthroline (0.9 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford (PCy₃)(C₁₂H₈N₂)₂(Cl)₂Ru═C═CHPh55 as an orange powder (1.7 gram, 94% yield).

¹H NMR (500 MHz, CD₂Cl₂): δ=6.98-10.18 (multiple peaks, 13H), 5.03 (d,1H, J=4 Hz, vinylidene peak), 0.95-2.70 (multiple peaks, 33H) ppm.

Synthesis of (PCy₃)(C₁₀H₈N₂)(Cl)₂Ru═C=CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-bipyridine (0.8 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford (PCy₃)(C₁₀H₈N₂)(Cl)₂Ru═C═CHPh56 as a green powder (1.6 gram, 94% yield).

Synthesis of (PCy₃)(C₁₈H₁₂N₂)₂(Cl)₂Ru═C═CHPh

Complex 44 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-biquinoline (1.2 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₈H₁₂N₂)₂(Cl)₂Ru═C═CHPh 57 as a purple powder (1.7 gram, 89%yield).

¹H NMR (300 MHz, C₆D₆): δ 6.88-9.15 (multiple peaks, 17H), 4.79 (d, 1H,J=3 Hz, vinylidene), 1.21-2.86 (multiple peaks, 33H) ppm.

Synthesis of (PCy₃)(C₉H₁₂N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 45 (2.0 grams) was dissolved in toluene (10 mL), and4-pyrrolidinopyridine (1.5 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₉H₁₂N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 58 as a dark green powder (1.8gram, 90% yield).

Synthesis of (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 45 (2.0 grams) was dissolved in toluene (10 mL), and4,4′-bipyridine (1.5 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 59 as a brown powder (1.7 gram, 81%yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0451 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about81.2° C. Result: Time to reach maximum temperature (T_(max))=349seconds. T_(max)=157.7° C.

Example (2)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0447 grams inthe presence of sIMesHCCl₃=0.0445 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 80.8° C. Result:Time to reach maximum temperature (T_(max))=189 seconds. T_(max)=208.4°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=95.70° C.

Synthesis of (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 45 (2.0 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.6 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 60 as a brown powder (1.7 gram, 81%yield).

¹H NMR (300 MHz, C₆D₆): δ=6.89-10.08 (multiple peaks, 18H), 4.17 (d, 1H,J=4 Hz, vinylidene), 1.25-2.74 (multiple peaks, 33H), 1.31 (s, 9H) ppm.

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0443 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about82.0° C. Result: Time to reach maximum temperature (T_(max))=208seconds. T_(max)=205.1° C. Glass transition temperature measured bythermal mechanical analysis (TMA)=54.42° C.

Example (2)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0445 grams inthe presence of sIMesHCCl₃=0.0449 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 81.1° C. Result:Time to reach maximum temperature (T_(max))=126 seconds. T_(max)=246.2°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=175.35° C.

Synthesis of (PCy₃)(C₁₂H₈N₂)(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 45 (2.0 grams) was dissolved in toluene (10 mL), and1,10-phenanthroline (0.9 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₂H₈N₂)(Cl)₂Ru═C═CH—C(CH₃)₃ 61 as an orange powder (1.5 gram,83% yield).

¹H NMR (300 MHz, C₆D₆): δ=6.90-10.73 (multiple peaks, 8H), 4.02 (d, 1H,J=3 Hz, vinylidene), 1.46-3.06 (multiple peaks, 33H), 1.62 (s, 9H) ppm.

Synthesis of (PCy₃)(C₁₀H₈N₂)(Cl)₂Ru═C═CH—C(CH₃)₃ Complex 45 (2.0 grams)was dissolved in toluene (10 mL), and 2,2′-bipyridine (0.8 grams) wasadded. The reaction flask was purged with argon and the reaction mixturewas stirred for approximately 12 hours at about 20° C. to about 25° C.After approximately 12 hours the reaction mixture was transferred into75 mL of cold (about 0° C.) pentane. The pentane mixture was filtered,washed with 4×20 mL of cold pentane, and dried under vacuum to afford(PCy₃)(C₁₀H₈N₂)(Cl)₂Ru═C═CH—C(CH₃)₃ 62 as an orange powder (1.3 gram,76% yield).

Synthesis of (PCy₃)(C₁₈H₁₂N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 45 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-biquinoline (1.3 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₈H₁₂N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 63 as a gray powder (1.1 gram, 58%yield).

Synthesis of (IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 46 (2.0 grams) was dissolved in toluene (10 mL), and4-pyrrolidinopyridine (1.4 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 64 as a gray powder (0.7 gram,35% yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (IMesH₂)(C₉H₁₂N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0456 grams ata DCPD:Ru ratio of (about 10,000:1) at a starting temperature of about80.7° C. Result: Time to reach maximum temperature (T_(max))=143seconds. T_(max)=170.5° C.

Synthesis of (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 46 (2.0 grams) was dissolved in toluene (10 mL), and4,4′-bipyridine (1.5 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 65 as a dark purple powder (2.0gram, 95% yield).

Example (1)

A 75 g mass of hexylnorbornene was polymerized using(IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0488 g at a H_(x)N:Ru reactantratio of (7,500:1) at a starting temperature of about 80.6° C. Result:Time to reach maximum temperature (T_(max))=183 seconds. T_(max)=191.7°C.

Example (2)

A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g ofDCPD (containing 24 wt % trimerized DCPD) and 37.5 g of hexylnorbornene,was polymerized using (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0549 g ata DCPD:Ru reactant ratio of (7,500:1) and H_(x)N:Ru reactant ratio of(7,500:1), by heating the mixture to a starting temperature of about80.3° C. Result: Time to reach maximum temperature (T_(max))=138seconds. T_(max)=181.9° C.

Synthesis of (IMesH₂)(C₁₁H₉N)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 46 (2.0 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.5 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₁₁H₉N)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 66 as a light brown powder (0.6gram, 29% yield).

Synthesis of (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 46 (2.0 grams) was dissolved in toluene (10 mL), and pyridine(0.8 grams) was added. The reaction flask was purged with argon and thereaction mixture was stirred for approximately 12 hours at about 20° C.to about 25° C. After approximately 12 hours the reaction mixture wastransferred into 75 mL of cold (about 0° C.) pentane. The pentanemixture was filtered, washed with 4×20 mL of cold pentane, and driedunder vacuum to afford (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 67 as ayellow powder (0.9 gram, 53% yield).

Synthesis of (IMesH₂)(C₁₀H₈N₂)(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 46 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-bipyridine (0.8 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₁₀H₈N₂)(Cl)₂Ru═C═CH—C(CH₃)₃ 68 as a brown powder (0.9 gram,53% yield).

Synthesis of (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 47 (2.0 grams) was dissolved in toluene (10 mL), and pyridine(0.7 grams) was added. The reaction flask was purged with argon and thereaction mixture was stirred for approximately 12 hours at about 20° C.to about 25° C. After approximately 12 hours the reaction mixture wastransferred into 75 mL of cold (about 0° C.) pentane. The pentanemixture was filtered, washed with 4×20 mL of cold pentane, and driedunder vacuum to afford (PCy₃)(C₅H₅N)₂(Cl)₂Ru═C═C=C(Ph)₂ 69 as a brownpowder (0.7 gram, 41% yield).

Synthesis of (PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 45 (2.0 grams) was dissolved in toluene (10 mL), and4-dimethylaminopyridine (1.2 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 70 as pink powder (1.6 gram, 84%yield).

¹H NMR (300 MHz, C₆D₆): δ=5.89-9.66 (multiple peaks, 8H), 4.14 (d, J=4Hz, vinylidene), 1.31-2.78 (multiple peaks, 45H), 1.40 (s, 9H) ppm.

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0410 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about81.2° C. Result: Time to reach maximum temperature (T_(max))=306seconds. T_(max)=189.6° C. Glass transition temperature measured bythermal mechanical analysis (TMA)=35.88° C.

Example (2)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃=0.0411 grams inthe presence of sIMesHCCl₃=0.0450 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 81.9° C. Result:Time to reach maximum temperature (T_(max))=161 seconds. T_(max)=246.5°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=169.56° C.

Synthesis of (IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃

Complex 46 (2.0 grams) was dissolved in toluene (10 mL), and4-dimethylaminopyridine (1.2 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═C═CH—C(CH₃)₃ 71 as a gray powder (0.9 gram,47% yield).

Synthesis of (PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 47 (2.0 grams) was dissolved in toluene (10 mL), and4-dimethylaminopyridine (1.1 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₇H₁₀N₂)₂(Cl)₂Ru═C═C=C(Ph)₂ 72 as a brown powder (1.3 gram, 68%yield).

Synthesis of (PCy₃)(C₁₂H₈N₂)(Cl)₂Ru═C═C=C(Ph)₂

Complex 47 (2.0 grams) was dissolved in toluene (10 mL), and1,10-phenanthroline (0.8 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₂H₈N₂)(Cl)₂Ru═C═C=C(Ph)₂ 73 as a red-brown powder (1.2 gram,67% yield).

Synthesis of (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 47 (2.0 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.4 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂ 74 as a dark purple powder (1.5 gram, 71%yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂=0.0499 grams in thepresence of sIMesHCCl₃=0.0447 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 83.8° C. Result:Time to reach maximum temperature (T_(max))=288 seconds. T_(max)=238.7°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=124.72° C.

Example (2)

A 75 g mass of hexylnorbornene was polymerized using(PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂=0.0536 g in the presence ofs-ImesHCCl₃=0.0478 g at a H_(x)N:Ru:s-ImesHCCl₃ reactant ratio of(7,500:1:2) at a starting temperature of 80.3° C. Result: Time to reachmaximum temperature (T_(max))=230 seconds. T_(max)=195.6° C.

Example (3)

A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g ofDCPD (containing 24 wt % trimerized DCPD) and 37.5 g of hexylnorbornene,was polymerized using (PCy₃)(C₁₁H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂=0.0599 g in thepresence of s-ImesHCCl₃=0.0536 g at a DCPD:Ru:s-ImesHCCl₃ reactant ratioof (7,500:1:2) and H_(x)N:Ru:s-ImesHCCl₃ reactant ratio of (7,500:1:2),by heating the mixture to a starting temperature of about 82.4° C.Result: Time to reach maximum temperature (T_(max))=178 seconds.T_(max)=220.8° C.

Synthesis of (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 47 (2.0 grams) was dissolved in toluene (10 mL), and4,4′-bipyridine (1.4 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C=C(Ph)₂ 75 as a red-brown powder (2.0 gram,95% yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (PCy₃)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C=C(Ph)₂=0.0500 grams in thepresence of sIMesHCCl₃=0.0448 grams at a DCPD:Ru:sIMesHCCl₃ ratio of(about 10,000:1:2) at a starting temperature of about 84.6° C. Result:Time to reach maximum temperature (T_(max))=190 seconds. T_(max)=224.7°C. Glass transition temperature measured by thermal mechanical analysis(TMA)=105.52° C.

Synthesis of (PCy₃)(C₉H₁₂N₂)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 47 (2.0 grams) was dissolved in toluene (10 mL), and4-pyrrolidinopyridine (1.3 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₉H₁₂N₂)₂(Cl)₂Ru═C═C=C(Ph)₂ 76 as a dark purple powder (1.4 gram,70% yield).

Synthesis of (PCy₃)(C₁₀H₈N₂)(Cl)₂Ru═C═C=C(Ph)₂

Complex 47 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-bipyridine (0.7 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(PCy₃)(C₁₀H₈N₂)(Cl)₂Ru═C═C=C(Ph)₂ 77 as a dark purple powder (1.1 gram,65% yield).

Synthesis of (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 48 (2.0 grams) was dissolved in toluene (10 mL), and pyridine(0.7 grams) was added. The reaction flask was purged with argon and thereaction mixture was stirred for approximately 12 hours at about 20° C.to about 25° C. After approximately 12 hours the reaction mixture wastransferred into 75 mL of cold (about 0° C.) pentane. The pentanemixture was filtered, washed with 4×20 mL of cold pentane, and driedunder vacuum to afford (IMesH₂)(C₅H₅N)₂(Cl)₂Ru═C═C=C(Ph)₂ 78 as ared-brown powder (0.9 gram, 53% yield).

¹H NMR (300 MHz, C₆D₆): δ=6.52-8.09 (multiple peaks, 20H), 4.00 (s, 4H,sIMes)1.00-2.28 (multiple peaks, 18H) ppm.

Synthesis of (IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 48 (2.0 grams) was dissolved in toluene (10 mL), and4-dimethylaminopyridine (1.0 grams) was added. The reaction flask waspurged with argon and the reaction mixture was stirred for approximately12 hours at about 20° C. to about 25° C. After approximately 12 hoursthe reaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₇H₁₀N₂)₂(Cl)₂Ru═C═C=C(Ph)₂ 79 as a red-brown powder (1.0 gram,53% yield).

Synthesis of (IMesH₂)(Cl₂H₉N₂)(Cl)₂Ru═C═C=C(Ph)₂

Complex 48 (2.0 grams) was dissolved in toluene (10 mL), and1,10-phenanthroline (0.8 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₁₂H₈N₂)(Cl)₂Ru═C═C=C(Ph)₂ 80 as a red powder (0.6 gram, 33%yield).

Synthesis of (IMesH₂)(Cl₁H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 48 (2.0 grams) was dissolved in toluene (10 mL), and4-phenylpyridine (1.3 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₁₁H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂ 81 as a brown powder (1.1 gram, 52%yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (IMesH₂)(Cl H₉N)₂(Cl)₂Ru═C═C=C(Ph)₂=0.0515 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about80.9° C. Result: Time to reach maximum temperature (T_(max))=275seconds. T_(max)=118.2° C.

Synthesis of (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C=C(Ph)₂

Complex 48 (2.0 grams) was dissolved in toluene (10 mL), and4,4′-bipyridine (1.3 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C=C(Ph)₂ 82 as a brown powder (1.9 gram, 90%yield).

Example (1)

A 75 gram mass of DCPD (containing about 24% trimerized DCPD) waspolymerized using (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C═C(Ph)₂=0.0512 grams at aDCPD:Ru ratio of (about 10,000:1) at a starting temperature of about80.1° C. Result: Time to reach maximum temperature (T_(max))=144seconds. T_(max)=138.8° C.

Example (2)

A 75 g mass of hexylnorbornene was polymerized using(IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C=C(Ph)₂=0.0552 g at a H_(x)N:Ru reactantratio of (7,500:1) at a starting temperature of about 80.3° C. Result:Time to reach maximum temperature (T_(max))=578 seconds. T_(max)=138.5°C.

Example (3)

A 75 g mass of a monomer mixture, prepared by mixing together 37.5 g ofDCPD (containing 24 wt % trimerized DCPD) and 37.5 g of hexylnorbornene,was polymerized using (IMesH₂)(C₁₀H₈N₂)₂(Cl)₂Ru═C═C=C(Ph)₂=0.0617 g at aDCPD:Ru reactant ratio of (7,500:1) and H_(x)N:Ru reactant ratio of(7,500:1), by heating the mixture to a starting temperature of about80.6° C. Result: Time to reach maximum temperature (T_(max))=259seconds. T_(max)=135.7° C.

Synthesis of (IMesH₂)(C₁₀H₈N₂)(Cl)₂Ru═C═C=C(Ph)₂

Complex 48 (2.0 grams) was dissolved in toluene (10 mL), and2,2′-bipyridine (0.7 grams) was added. The reaction flask was purgedwith argon and the reaction mixture was stirred for approximately 12hours at about 20° C. to about 25° C. After approximately 12 hours thereaction mixture was transferred into 75 mL of cold (about 0° C.)pentane. The pentane mixture was filtered, washed with 4×20 mL of coldpentane, and dried under vacuum to afford(IMesH₂)(C₁₀H₈N₂)(Cl)₂Ru═C═C=C(Ph)₂ 83 as a red-brown powder (1.3 gram,76% yield).

¹H NMR (300 MHz, C₆D₆): δ=6.60-7.85 (multiple peaks, 18H), 4.00 (s, 4H,sIMes)1.08-2.60 (multiple peaks, 18H) ppm.

What is claimed is:
 1. A compound of the formula:

wherein M is ruthenium or osmium; X and X¹ are the same or different andare each independently any anionic ligand; L, L^(1′), and L² are thesame or different and are each independently any neutral electron donorligand; R and R¹ the same or different and are each independentlyhydrogen or a substituted or unsubstituted substituent selected from thegroup consisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl,C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy,aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl,C₁-C₂₀ alkylsulfinyl, and silyl.
 2. The compound of claim 1 wherein atleast one of the R and R¹ substituent group is substituted with one ormore moieties selected from the group consisting of C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, and aryl, and wherein the moiety is substituted orunsubstituted.
 3. The compound of claim 2 wherein the moiety issubstituted with one or more groups selected from the group consistingof halogen, a C₁-C₅ alkyl, C₁-C₅ alkoxy, and phenyl.
 4. The compound ofclaim 1 wherein R is hydrogen and R¹ is selected from the groupconsisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and aryl.
 5. The compound ofclaim 4 wherein R¹ is phenyl or vinyl.
 6. The compound of claim 1wherein X and X¹ are each independently hydrogen, halide, or selectedfrom the group consisting of C₁-C₂₀ alkyl, aryl, C₁-C₂₀ alkoxide,aryloxide, C₃-C₂₀ alkyldiketonate, aryldiketonate, C₁-C₂₀ carboxylate,arylsulfonate, C₁-C₂₀ alkylsulfonate, C₁-C₂₀ alkylthio, C₁-C₂₀alkylsulfonyl, or C₁-C₂₀ alkylsulfinyl, wherein X and X¹ is eachindependently substituted or unsubstituted.
 7. The compound of claim 6wherein at least one of X and X¹ is substituted with one or moremoieties selected from the group consisting of C₁-C₁₀ alkyl, C₁-C₁₀alkoxy, and aryl, wherein the moiety is substituted or unsubstituted. 8.The compound of claim 7 wherein the moiety is substituted with one ormore groups selected from the group consisting of halogen, C₁-C₅ alkyl,C₁-C₅ alkoxy, and phenyl.
 9. The compound of claim 1 wherein X and X¹are each independently selected from the group consisting of halide,benzoate, C₁-C₅ carboxylate, C₁-C₅ alkyl, phenoxy, C₁-C₅ alkoxy, C₁-C₅alkylthio, aryl, and C₁-C₅ alkyl sulfonate.
 10. The compound of claim 9wherein X and X¹ are each independently selected from the groupconsisting of halide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO,(CF₃)(CH₃)₂CO, PhO, MeO, EtO, tosylate, mesylate, andtrifluoromethanesulfonate.
 11. The compound of claim 1 wherein L, L^(1′)and L² are each independently selected from the group consisting of amonodentate, bidentate and tetradentate neutral electron donor ligand.12. The compound of claim 11 wherein L, L^(1′) and L² are eachindependently selected from the group consisting of phosphine,sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine,stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl,pyridine, thioether, N-heterocyclic carbene ligand and any derivativestherefrom.
 13. The compound of claim 1 wherein both L^(1′) and L² areeither the same or different N-heterocyclic carbene ligands.
 14. Thecompound of claim 1 wherein the N-heterocyclic carbene ligand isselected from the group consisting of:

wherein R, R¹, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are each independentlyhydrogen or a substituted or unsubstituted substituent selected from thegroup consisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, aryl,C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy,aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyland C₁-C₂₀ alkylsulfinyl.
 15. The compound of claim 1 wherein L is anN-heterocyclic carbene ligand or a phosphine, and L^(1′) and L² are eachheterocyclic ligands.
 16. The compound of claim 15 wherein at least oneof L^(1′) and L² is aromatic.
 17. The compound of claim 15 whereinL^(1′) and L² together form a bidenatate ligand.
 18. The compound ofclaim 1 at least one of L^(1′) and L² is a unsubstituted or substitutedheteroarene selected from the group consisting of furan, thiophene,pyrrole, pyridine, bipyridine, picolylimine, gamma-pyran,gamma-thiopyran, phenanthroline, pyrimidine, bipyrimidine, pyrazine,indole, coumarone, thionaphthene, carbazole, dibenzofuran,dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole,dithiazole, isoxazole, isothiazole, quinoline, bisquinoline,isoquinoline, bisisoquinoline, acridine, chromene, phenazine,phenoxazine, phenothiazine, triazine, thianthrene, purine, bisimidazoleand bisoxazole.
 19. The compound of claim 18 wherein at least one ofL^(1′) and L² is a substituted or unsubstituted pyridine or asubstituted or unsubstituted pyridine derivative.
 20. The compound ofclaim 18 wherein the substituted or unsubstituted heteroarene isselected from the group consisting of:


21. The compound of claim 1 wherein at least one of L^(1′) and L² is aunsubstituted or substituted heterocycle selected from the groupconsisting of:

wherein R is selected from the group consisting of C₁-C₂₀ alkyl, aryl,ether, amide, halide, nitro, ester, pyridyl.
 22. A compound of theformula:

wherein M is ruthenium; X and X¹ are each independently selected fromthe group consisting of halide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO,(CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO, MeO, EtO, tosylate, mesylate, andtrifluoromethanesulfonate; L is any neutral electron donor ligand;L^(1′) and L² are the same or different and are each a substituted orunsubstituted heteroarene, and wherein L^(1′) and L² may be joined, R ishydrogen and R¹ is selected from the group consisting of C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, and aryl.
 23. The compound of claim 22 wherein X and X¹are each Cl, L is (IMesH₂), L^(1′) and L² are each independently apyridine or pyridine derivative; R is hydrogen and R¹ is phenyl orvinyl.
 24. A compound selected from the group consisting of:

wherein sIMES is


25. A compound of the formula:

wherein M is ruthenium or osmium; X and X¹ are the same or different andare each independently any anionic ligand; L, L^(1′), and L² are thesame or different and are each independently any neutral electron donorligand; R is hydrogen or a substituted or unsubstituted substituentselected from the group consisting of C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl,C₂-C₂₀ alkynyl, aryl, C₁-C₂₀ carboxylate, C₁-C₂₀ alkoxy, C₂-C₂₀alkenyloxy, C₂-C₂ alkynyloxy, aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀alkylthio, C₁-C₂₀ alkylsulfonyl and C₁-C₂₀ alkylsulfinyl; R¹ issubstituted or unsubstituted C₂-C₂₀ alkenyl.
 26. The compound of claim25 wherein R¹ is substituted or unsubstituted vinyl.
 27. The compound ofclaim 1 wherein at least one of L, L^(1′) and L² is an N-heterocycliccarbene ligand.